Ampholytic copolymer and use thereof

ABSTRACT

The present invention relates to an ampholytic copolymer, to polyelectrolyte complexes which comprise such an ampholytic copolymer, and to cosmetic or pharmaceutical compositions which comprise at least one ampholytic copolymer or one polyelectrolyte complex.

This application is a National Stage filing of PCT/EP2003/014944 filedDec. 29, 2003 which in turn claims priority from German Application 10261 750.3, filed Dec. 30, 2002.

The present invention relates to an ampholytic copolymer, topolyelectrolyte complexes which comprise such an ampholytic copolymer,and to cosmetic or pharmaceutical compositions which comprise at leastone ampholytic copolymer or one polyelectrolyte complex.

Polymers with a relatively large number of ionically dissociatablegroups in the main chain and/or a side chain are referred to aspolyelectrolytes. If these polymers have both anionogenic/anionic andalso cationogenic/cationic groups, then they are amphotericpolyelectrolytes or ampholytic polymers. An ionogenic or ionic polymercan react with an oppositely chargeable or charged polymer to form apolyelectrolyte complex (symplex). Ampholytic polymers can in principleform such polyelectrolyte complexes with anionogenic/anionic,cationogenic/cationic and/or at least one further ampholytic polymer.Polyelectrolytes with an adequate number of dissociatable groups arewater-soluble or water-dispersible and have found diverse uses in thefield of coatings, papermaking auxiliaries, in textile manufacture, andspecifically in pharmacy and cosmetics.

Cosmetically and pharmaceutically acceptable water-soluble polymersserve, for example in soaps, creams and lotions, as formulating agents,e.g. as thickener, foam stabilizer or water absorbent or else toalleviate the irritative effect of other ingredients or to improve thedermal application of active ingredients. Their object in hair cosmeticsconsists in influencing the properties of the hair. In pharmacy, theyserve, for example, as coatings or binders for solid medicaments.

For hair cosmetics, film-forming polymers wit ionic groups are used, forexample, as conditioner in order to improve the dry and wet combability,the feel to the touch, the shine and the appearance of the hair, andalso to impart antistatic properties to the hair. The structure and modeof action of various hair-treatment polymers are described in Cosmetic &Toiletries 103 (1988) 23. Depending on the intended use, water-solublepolymers with cationic functionalities are used which have a highaffinity to the negatively charged surface of the hair, which arises dueto its structure. Standard commercial cationic conditioner polymers are,for example, cationic hydroxyethylcellulose, cationic polymers based onN-vinylpyrrolidone, e.g. copolymers of N-vinylpyrrolidone andquarternized N-vinyl-imidazole, acrylamide and diallyldimethylammoniumchloride. Water-soluble polymers with anionic functionalities, such as,for example, optionally crosslinked polyacrylic acid, serve, forexample, as thickener and also carboxylate-group-containing polymers areused, for example, for creating hairstyles.

The provision of products with a complex profile of properties oftenpresents problems. For example, there is a need for polymers forcosmetic compositions which are able to form essentially smooth,tack-free films which impart a pleasant feel to the hair and to the skinand at the same time have a good conditioning action or setting action.Requirements of hair-setting resins are, for example, strong hold athigh atmospheric humidity, elasticity, ability to be washed out of thehair, compatibility in the formulation and a pleasant feel of the hairtreated therewith. In addition, aesthetic requirements are increasinglyplaced on cosmetic and pharmaceutical products by the consumer. Forexample, in the case of such products, a preference for clear, opaqueformulations in the form of gels is currently observed. In many cases,the desired profile of properties can only be achieved through the useof two or more polymers with anionic groups. In this connection,however, an incompatibility of the various polymers with one anotheroften arises, which can, for example, lead to undesired salting out.There is therefore a need for cosmetically and pharmaceuticallycompatible polyelectrolytes which, when used as the sole polymercomponent, are suitable for providing a certain profile of propertiesand/or which are compatible with a large number of differentpolyelectrolytes.

EP-A-0 100 890 describes copolymers obtained by free-radicalcopolymerization of

-   a) 20 to 75 parts by weight of at least one C₂-C₂₀-alkyl ester of    (meth)acrylic acid,-   b) 5 to 50 parts by weight of at least one nitrogen-containing,    neutrally reacting water-soluble monomer,-   c) 1 to 25 parts by weight of at least one monomer containing    cationic groups and-   d) 1 to 25 parts by weight of at least one olefinically unsaturated    C₃-C₅-carboxylic acid which is copolymerizable with a), b) and c).

WO 01/62809 describes a cosmetic composition which comprises at leastone water-soluble or water-dispersible polymer, which comprises, inincorporated form,

-   a) 5 to 50% by weight of at least one α,β-ethylenically unsaturated    monomer with a tert-butyl group,-   b) 25 to 90% by weight of at least one N-vinylamide and/or    N-vinyllactam,-   c) 0.5 to 30% by weight of at least one compound with a    free-radically polymerizable, α,β-ethylenically unsaturated double    bond and at least one cationogenic and/or cationic group per    molecule, and-   d) 0 to 30% by weight of at least one further α,β-ethylenically    unsaturated compound, which may be compounds with at least one    anionogenic and/or anionic group per molecule.

EP-A-1038891 describes water-soluble or water-dispersible polymericsalts of at least one polymer and at least one oppositely chargedneutralizing agent, where the polymer and the neutralizing agent eachhas only one type of ionic group.

WO 00/39176 describes a hydrophilic cationic ampholytic copolymer whichcomprises, in copolymerized form, 0.05 to 20 mol % of an anionic monomerwith at least one carboxyl group and 10 to 45 mol % of a cationicmonomer with at least one amino group, where the molar ratio of cationicmonomer to anionic monomer is about 2:1 to 16:1. These ampholyticcopolymers can be used, inter alia, for modifying the rheologicalproperties of bodycare compositions. In the working examples, use ismade exclusively of polymers based on methacrylic acid anddimethylaminopropylmethacrylamide, and of acrylic acid anddimethylaminoethyl methacrylate.

It is an object of the present invention to provide novelpolyelectrolytes which are suitable for use in cosmetic andpharmaceutical compositions. They should either, when used as the solepolymer component, be suitable for conferring a complex spectrum ofrequirements and, for example, be able to form tack-free smooth films,have a good setting action and be suitable for the preparation ofproducts in the form of gels, or be compatible with the greatestpossible number of different polyelectrolytes for cosmetic andpharmaceutical applications.

We have found that this object is achieved by ampholytic copolymerswhich comprise, in incorporated form, at least one monomer having atleast one anionogenic and/or anionic group per molecule, at least onemonomer having at least one cationogenic and/or cationic group permolecule and at least one hydrophilic monomer having an amide group.

The invention therefore provides an ampholytic copolymer obtainable byfree-radical copolymerization of

-   a) at least one compound with a free-radically polymerizable,    α,β-ethylenically unsaturated double bond and at least one    anionogenic and/or anionic group per molecule,-   b) at least one compound with a free-radically polymerizable,    α,β-ethylenically unsaturated double bond and at least one    cationogenic and/or cationic group per molecule,-   c) at least one hydrophilic α,β-ethylenically unsaturated    amide-group-containing compound of the formula I

-   -   in which    -   one of the radicals R¹ to R³ is a group of the formula CH₂═CR⁴—        where R⁴═H or C₁-C₄-alkyl, and the other radicals R¹ to R³,        independently of one another, are H, alkyl, cycloalkyl,        heterocycloalkyl, aryl or hetaryl,    -   where R¹ and R² together with the amide group to which they are        bonded may also be a lactam with 5 to 8 ring atoms,    -   where R² and R³ together with the nitrogen atom to which they        are bonded may also be a five- to seven-membered heterocycle,    -   with the proviso that the sum of the carbon atoms of the        radicals R¹, R² and R³ is at most 8.

For the purposes of the present invention, the expression alkyl includesstraight-chain and branched alkyl groups. Suitable short-chain alkylgroups are, for example, straight-chain or branched C₁-C₇-alkyl groups,preferably C₁-C₆-alkyl groups and particularly preferably C₁-C₄-alkylgroups. These include, in particular, methyl, ethyl, propyl, isopropyl,n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl,3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl etc.

Suitable longer-chain C₈-C₃₀-alkyl or C₈-C₃₀-alkenyl groups arestraight-chain and branched alkyl or alkenyl groups. Preferably, theseare predominantly linear alkyl radicals, as also arise in natural orsynthetic fatty acids and fatty alcohols and also oxo alcohols, whichmay optionally be additionally mono-, di- or polyunsaturated.

These include, for example, n-hexyl(ene), n-heptyl(ene), n-octyl(ene),n-nonyl(ene), n-decyl(ene), n-undecyl(ene), n-dodecyl(ene),n-tridecyl(ene), n-tetradecyl(ene), n-pentadecyl(ene), n-hexadecyl(ene),n-heptadecyl(ene), n-octadecyl(ene), n-nonadecyl(ene) etc.

Cycloalkyl is preferably C₅-C₈-cycloalkyl, such as cyclopentyl,cyclohexyl, cycloheptyl or cyclooctyl.

Aryl includes unsubstituted and substituted aryl groups and ispreferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl,anthracenyl, phenanthrenyl, naphthacenyl and in particular is phenyl,tolyl, xylyl or mesityl.

In the text below, compounds which can be derived from acrylic acid andmethacrylic acid are sometimes referred to in shortened form by addingthe syllable “(meth)” to the compound derived from acrylic acid.

The ampholytic copolymers and polyelectrolyte complexes according to theinvention can advantageously be formulated as gels under standardconditions (20° C.). “Gel-like consistency” is shown by compositionswhich have a higher viscosity than a liquid and which areself-supporting, i.e. they retain the shape given to them without ashape-stabilizing coating. In contrast to solid formulations, however,gel-like formulations can be readily deformed under the application ofshear forces. The viscosity of the gel-like compositions is preferablyin a range of greater than 600 to about 60 000 mPas. The gels arepreferably hair gels which have a viscosity of preferably 6000 to 30 000mPas.

For the purposes of the present invention, water-soluble monomers andpolymers are understood as meaning monomers and polymers which dissolvein an amount of at least 1 g/l at 20° C. in water. Water-dispersiblemonomers and polymers are understood as meaning monomers and polymerswhich disintegrate into dispersible particles under the application ofshear forces, for example by stirring. Hydrophilic monomers arepreferably water-soluble or at least water-dispersible. The copolymersand polyelectrolyte complexes according to the invention are generallywater-soluble or at least water-dispersible.

The ampholytic copolymers according to the invention have bothanionogenic and/or anionic groups, and also cationogenic and/or cationicgroups. For their preparation, preference is given to using monomerswith initially uncharged, i.e. with anionogenic and cationogenic groups.In a suitable embodiment these monomers are used together, i.e. in theform of “salt pairs”. Preference here is given to using at least some ofthe compounds a) and b) in the form of a monomer composition, where, forthis monomer composition, the molar ratio of anionogenic and anionicgroups of component a) to cationogenic and cationic groups of componentb) is about 1:1.

If desired, for the preparation of the ampholytic copolymers accordingto the invention, monomers which are already charged, i.e. monomers withanionic and cationic groups, can also be used instead of unchargedmonomers or in addition to uncharged monomers or in addition to saltpairs. The counter ions which carry these monomers are then preferablyderived from acids or bases, as are described below for adjusting the pHduring the polymerization or of the resulting polymers. Cationicmonomers may also be used in partially or completely quaternized form.

Preferably, the quantitative molar ratio of compounds a) to compounds b)(i.e. of anionogenic/anionic compounds to cationogenic/cationiccompounds) is in a range from 0.5:1 to less than 2:1 and in particularin a range from 0.7:1 to 1.8:1.

In a suitable embodiment, the ampholytic copolymers according to theinvention are outwardly essentially electroneutral. Such copolymershave, bonded to the polymer backbone, anionic and cationic groups inquantitative ratios such that positive and negative charges areessentially balanced. Preferably, the ratio of positive to negativecharge equivalents is in a range from 0.8:1 to 1:0.8, particularlypreferably 0.9:1 to 1:0.9 and specifically 0.95:1 to 1:0.95.

The pH of a 0.1 molar aqueous solution of the water-soluble ampholyticcopolymers according to the invention at a temperature of 20° C. ispreferably in a range from 5.5 to 8.0, particularly preferably from 5.6to 7.5 and in particular from 5.8 to 7.3. Since the ampholyticcopolymers according to the invention generally act as buffers, the pHvalues of their aqueous solutions are generally relatively stable towarddilution and the addition of acids or bases within a wide range.

In the preparation of the ampholytic copolymers according to theinvention by free-radical copolymerization in an aqueous medium, the pHis preferably in a range from 5.5 to 9.0, particularly preferably from5.6 to 8.5 and in particular from 5.8 to 7.5. The pH can be adjustedfirstly through appropriate choice of the monomers with anionogenic andcationogenic groups used for the copolymerization. In addition, the pHcan be adjusted to the desired value by adding at least one acid or atleast one base.

In the preparation of the ampholytic copolymers according to theinvention by free-radical copolymerization in nonaqueous media, forexample by precipitation polymerization, the monomers are likewisepreferably chosen such that the pH of a corresponding aqueous solutionis in a range from 5.5 to 8.0, particularly preferably from 5.6 to 7.5and in particular from 5.8 to 7.3, or an acid or base is added, in orderto adjust the pH of a corresponding aqueous solution to a value withinthis range.

The pH is adjusted by adding at least one suitable acid, e.g. acarboxylic acid, such as lactic acid or tartaric acid, or a mineralacid, such as phosphoric acid, sulfuric acid or hydrochloric acid or byadding at least one suitable base, preferably an alkali metal hydroxide,such as NaOH or KOH, ammonia or an amine, such as triethylamine and inparticular an aminoalcohol, such as triethanolamine,methyldiethanolamine, dimethylethanolamine or 2-amino-2-methylpropanol.

The ampholytic copolymer according to the invention preferablycomprises, in copolymerized form 0.1 to 25% by weight, particularlypreferably 0.5 to 20% by weight, based on the total weight of thecomponents used for the polymerization, of at least one compound a).

The compounds a) are preferably chosen from monoethylenicallyunsaturated carboxylic acids, sulfonic acids, phosphonic acids andmixtures thereof.

The monomers a) include monoethylenically unsaturated mono- anddicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms,which may also be used in the form of their salts or anhydrides.Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid,α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride,itaconic acid, citraconic acid, mesaconic acid, glutaconic acid,aconitic acid and fumaric acid. The monomers a) also include thehalf-esters of monoethylenically unsaturated dicarboxylic acids having 4to 10, preferably 4 to 6, carbon atoms, e.g. of maleic acid, such asmonomethyl maleate. The monomers a) also include monoethylenicallyunsaturated sulfonic acids and phosphonic acids, for examplevinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethylmethacrylate, sulfopropyl acrylate, sulfopropyl methacrylate,2-hydroxy-3-acryloxypropylsulfonic acid,2-hydroxy-3-methacryloxypropylsulfonic acid, styrene sulfonic acid,2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid andallylphosphonic acid. The monomers a) also include the salts of theabovementioned acids, in particular the sodium, potassium and ammoniumsalts, and also the salts with the abovementioned amines. The monomersa) can be used as such or as mixtures with one another. The proportionsby weight given all refer to the acid form.

Component a) is preferably chosen from acrylic acid, methacrylic acid,ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid,maleic anhydride, fumaric acid, itaconic acid, citraconic acid,mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

Component a) is particularly preferably chosen from acrylic acid,methacrylic acid, itaconic acid and mixtures thereof.

Furthermore, component a) is particularly preferably chosen from2-acrylamido-2-methyl-1-propanesulfonic acid, styrenesulfonic acid,vinylsulfonic acid, vinyl-phosphonic acid, mixtures thereof and mixtureswith the abovementioned monomers a). In particular, use is made of2-acrylamido-2-methylpropanesulfonic acid as the sole compound ofcomponent a), or mixtures which contain2-acrylamido-2-methylpropanesulfonic acid.

The ampholytic copolymer comprises, in copolymerized form, preferably0.1 to 40% by weight, particularly preferably 0.5 to 35% by weight, inparticular 1 to 30% by weight, based on the total weight of thecomponents used for the polymerization, of at least one compound ofcomponent b).

The cationogenic and/or cationic groups of component b) are preferablynitrogen-containing groups, such as primary, secondary and tertiaryamino groups, and also quaternary ammonium groups. Thenitrogen-containing groups are preferably tertiary amino groups orquaternary ammonium groups. Charged cationic groups can be produced fromthe amine nitrogens either by protonation, e.g. with monobasic orpolybasic carboxylic acids, such as lactic acid, or tartaric acid, ormineral acids, such as phosphoric acid, sulfuric acid and hydrochloricacid, or by quaternization, e.g. with alkylating agents, such asC₁-C₄-alkyl halides or sulfates. Examples of such alkylating agents areethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethylsulfate and diethyl sulfate.

Suitable compounds b) are, for example, the esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids with aminoalcohols. Preferredaminoalcohols are C₂-C₁₂-aminoalcohols which are C₁-C₈-dialkylated onthe amine nitrogen. Suitable as acid component of these esters are, forexample, acrylic acid, methacrylic acid, fumaric acid, maleic acid,itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate andmixtures thereof. Preference is given to using acrylic acid, methacrylicacid and mixtures thereof. Preference is given toN,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl(meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.

Suitable monomers b) are also the amides of the abovementionedα,β-ethylenically unsaturated mono- and dicarboxylic acids with diamineswhich have at least one primary or secondary amino group. Preference isgiven to diamines which have a tertiary and a primary or secondary aminogroup. The monomers b) used are preferablyN-[2-(dimethylamino)ethyl]acrylamide,N-[2-(dimethylamino)ethyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)propyl]methacrylamide,N-[4-(dimethylamino)butyl]acrylamide,N-[4-(dimethylamino)butyl]methacrylamide,N-[2-(diethylamino)ethyl]acrylamide,N-[4-(dimethylamino)cyclohexyl]acrylamide,N-[4-(dimethylamino)cyclohexyl]methacrylamide etc. Particular preferenceis given to using N-[3-(dimethylamino)propyl]acrylamide and/orN-[3-(dimethylamino)propyl]methacrylamide.

Suitable monomers b) are also N,N-diallylamines andN,N-diallyl-N-alkylamines and their acid addition salts andquaternization products. Alkyl is here preferably C₁-C₂₄-alkyl.Preference is given to N,N-diallyl-N-methylamine andN,N-diallyl-N,N-dimethylammonium compounds, such as, for example, thechlorides and bromides.

Suitable monomers b) are also vinyl- and allyl-substituted nitrogenheterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole,vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Component b) is preferably chosen from N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, vinylimidazoleand mixtures thereof.

Preferred combinations of components a) and b) which can be used, forexample, as salt pair for the free-radical copolymerization are(meth)acrylic acid/N,N-dimethylaminopropyl (meth)acrylate and(meth)acrylic acid/vinylimidazole.

Further preferred combinations of components a) and b) are:

-   -   2-acrylamido-2-methylpropanesulfonic acid and    -   at least one monomer chosen from        N-[3-dimethylamino)propyl]methacrylamide, vinylimidazole,        N-(tert-butyl)aminoethyl (meth)acrylate, N,N-diallylamine,        N,N-diallyl-N-methylamine and mixtures thereof.

Further preferred combinations of components a) and b) are:

-   -   styrenesulfonic acid and    -   at least one monomer chosen from        N-[3-(dimethylamino)propyl]methacrylamide, vinylimidazole,        N-(tert-butyl)aminoethyl (meth)acrylate, N,N-diallylamine,        N,N-diallyl-N-methyl-amine and mixtures thereof.

Further preferred combinations of components a) and b) are:

-   -   vinylsulfonic acid and    -   at least one monomer chosen from        N-[3-(dimethylamino)propyl]methacrylamide, vinylimidazole,        N-(tert-butyl)aminoethyl (meth)acrylate, N,N-diallylamine,        N,N-diallyl-N-methylamine and mixtures thereof.

Further preferred combinations of components a) and b) are:

-   -   vinylphosphonic acid and    -   at least one monomer chosen from        N-[3-(dimethylamino)propyl]methacrylamide, vinylimidazole,        N-(tert-butyl)aminoethyl (meth)acrylate, N,N-diallylamine,        N,N-diallyl-N-methylamine and mixtures thereof.

The ampholytic copolymer according to the invention comprises, incopolymerized form, preferably 40 to 99.8% by weight, particularlypreferably 45 to 99% by weight, in particular 50 to 98% by weight, basedon the total weight of the components used for the polymerization, of atleast one compound c).

The compounds of component c) preferably have at most 7 further carbonatoms in addition to the carbonyl carbon atom of the amide group.

Preferably, the compounds of component c) are chosen from primary amidesof α,β-ethylenically unsaturated monocarboxylic acids, N-vinylamides ofsaturated monocarboxylic acids, N-vinyllactams, N-alkyl- andN,N-dialkylamides of α,β-ethylenically unsaturated monocarboxylic acidsand mixtures thereof.

Suitable N-alkyl- and N,N-dialkylamides of α,β-ethylenically unsaturatedmonocarboxylic acids which have at most 8 further carbon atoms inaddition to the carbonyl carbon atom of the amide group are, forexample, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide,N-propyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide,N-tert-butyl(meth)acrylamide, N,N-dimethyl(meth)-acrylamide,N,N-diethyl(meth)acrylamide, piperidinyl(meth)acrylamide,morpholinyl(meth)acrylamide and mixtures thereof.

Particularly preferably, the compounds of component c) are chosen fromacrylamide, methacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam,N-vinylformamide, N-vinylacetamide and mixtures thereof.

The water-soluble or water-dispersible copolymers according to theinvention can, if desired, comprise, in copolymerized form, up to 20% byweight, preferably up to 15% by weight, particularly preferably 0.1 to10% by weight, of at least one further monomer d). Preferably, theseadditional monomers are chosen from esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids with C₁-C₃₀-alkanols andC₁-C₃₀-alkanediols, amides of α,β-ethylenically unsaturated mono- anddicarboxylic acids with C₂-C₃₀-aminoalcohols which have a primary orsecondary amino group, N-alkyl- and N,N-dialkylamide ofα,β-ethylenically unsaturated monocarboxylic acids which, in addition tothe carbonyl carbon atom of the amide group, have more than 8 furthercarbon atoms, esters of vinyl alcohol and allyl alcohol withC₁-C₃₀-monocarboxylic acids, vinyl ethers, vinylaromatics, vinylhalides, vinylidene halides, C₁-C₈-monoolefins, nonaromatic hydrocarbonswith at least two conjugated double bonds, siloxane macromers andmixtures thereof.

Preferred monomers d) are esters of α,β-ethylenically unsaturated mono-and dicarboxylic acids with C₈-C₃₀-alkanoles and C₈-C₃₀-alkanediols,particularly preferably with C₁₂-C₂₂-alkanoles and C₁₂-C₂₂-alkanedioles.

Preferably monomer d) is chosen from methyl (meth)acrylate, methylethacrylate, ethyl (meth)acrylate, ethyl ethacrylate, tert-butylethacrylate, n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl(meth)acrylate, ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate,n-decyl (meth)acrylate, n-undecyl (meth)acrylate, tridecyl(meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate,palmityl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl(meth)acrylate, arrachinyl (meth)acrylate, behenyl (meth)acrylate,lignocerenyl (meth)acrylate, cerotinyl (meth)acrylate, linolyl(meth)acrylate, palmitoleinyl (meth)acrylate, oleyl (meth)acrylate,linolyl (meth)acrylate, linolenyl (meth)acrylate, stearyl(meth)acrylate, lauryl (meth)acrylate, tert-butyl(meth)acrylamide,n-octyl(meth)acrylamide, 1,1,3,3-tetramethylbutyl(meth)acrylamide,ethylhexyl-(meth)acrylamide, n-nonyl(meth)acrylamide,n-decyl(meth)acrylamide, n-undecyl(meth)acrylamide,tridecyl(meth)acrylamide, myristyl(meth)acrylamide,pentadecyl(meth)acrylamide, palmityl(meth)acrylamide,heptadecyl-(meth)acrylamide, nonadecyl(meth)acrylamide,arrachinyl(meth)acrylamide, behenyl(meth)acrylamide,lignocerenyl(meth)acrylamide, cerotinyl(meth)acryl-amide,melissinyl(meth)acrylamide, palmitoleinyl(meth)acrylamide,oleyl(meth)acrylamide, linolyl(meth)acrylamide,linolenyl(meth)acrylamide, stearyl(meth)acrylamide,lauryl(meth)acrylamide and mixtures thereof. Particular preference isgiven to the esters of α,β-ethylenically unsaturated mono- anddicarboxylic acids with linear C₁-C₃₀-alkanols.

Preferred monomers d) are also 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate,2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate,4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexylacrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate,3-hydroxy-2-ethylhexyl methacrylate etc.

The ampholytic copolymers according to the invention can additionallycomprise, in copolymerized form, a surface-active monomer e) differentfrom the components a) to d) and copolymerizable therewith.

Suitable monomers e) are polyether acylates, which, for the purposes ofthis invention, are generally understood as meaning esters ofα,β-ethylenically unsaturated mono- and dicarboxylic acids withpolyetherols. Suitable polyetherols are linear or branched substanceswhich have terminal hydroxyl groups and contain ether bonds. Generally,they have a molecular weight in the range from about 150 to 20 000.Suitable polyetherols are polyalkylene glycols, such as polyethyleneglycols, polypropylene glycols, polytetrahydrofurans and alkylene oxidecopolymers. Suitable alkylene oxides for the preparation of alkyleneoxide copolymers are, for example, ethylene oxide, propylene oxide,epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxidecopolymers can contain the copolymerized alkylene oxide units in randomdistribution or in the form of blocks. Preference is given to ethyleneoxide/propylene oxide copolymers.

As component e), preference is given to polyether acrylates of theformula II

in which

-   the order of the alkylene oxide units is arbitrary,-   k and l, independently of one another, are an integer from 0 to    1000, where the sum of k and l is at least 5,-   R^(a) is hydrogen, C₁-C₃₀-alkyl or C₅-C₈-cycloalkyl,-   R^(b) is hydrogen or C₁-C₈-alkyl,-   Y is O or NR^(b), where R^(b) is hydrogen, C₁-C₃₀-alkyl or    C₅-C₈-cycloalkyl.

Preferably, k is an integer from 1 to 500, in particular 3 to 250. l ispreferably an integer from 0 to 100.

R^(b) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particularhydrogen, methyl or ethyl.

R^(a) in the formula II is preferably C₈-C₃₀-alkyl, in particularC₁₂-C₃₀-alkyl, such as decyl, undecyl, tridecyl, myristyl, pentadecyl,palmityl, lauryl, stearyl, etc.

Y in the formula II is preferably O or NH.

Suitable polyether acrylates e) are, for example, the polycondensationproducts of the abovementioned α,β-ethylenically unsaturated mono-and/or dicarboxylic acids and acid chlorides, amides and anhydridesthereof with polyetherols. Suitable polyetherols can be prepared easilyby reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrinwith a starter molecule, such as water or a short-chain alcoholR^(a)—OH. The alkylene oxides can be used individually, alternately oras a mixture. Suitable polyether acrylates e) can also be prepared bytransesterification of the esters, described above as component d), ofα,β-ethylenically unsaturated mono- and dicarboxylic acids withpolyetherols. In this process, product mixtures generally result whichcontain both the esters used as starting materials and also thepolyether acrylates formed as a result of transesterification. Thesemixtures can generally be used for the preparation of the ampholyticcopolymers according to the invention without prior separation. Thepolyether acrylates e) can be used on their own or in mixtures for thepreparation of the polymers used according to the invention.

The ampholytic copolymers according to the invention preferably compriseup to 25% by weight, particularly preferably up to 20% by weight, inparticular up to 15% by weight, based on the total weight of themonomers used for the polymerization, of at least one monomer e) incopolymerized form. If a monomer e) is used, then it is done sopreferably in an amount of at least 0.1% by weight, particularlypreferably at least 1% by weight and in particular at least 5% byweight.

The ampholytic copolymers according to the invention can, if desired,comprise, in copolymerized form, at least one crosslinker f), i.e. acompound with two or more than two ethylenically unsaturated doublebonds. Preference is given to using crosslinkers f) in an amount from0.01 to 10% by weight, particularly preferably 0.03 to 3% by weight, inparticular 0.1 to 1% by weight, based on the total weight of thecomponents used for the polymerization.

Crosslinking monomers f) which can be used are compounds with at leasttwo ethylenically unsaturated double bonds, such as, for example, estersof ethylenically unsaturated carboxylic acids, such as acrylic acid ormethacrylic acid and polyhydric alcohols, ethers of at least dihydricalcohols, such as, for example, vinyl ethers or allyl ethers.

Examples of the parent alcohols are dihydric alcohols, such as1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol,1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol,1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol,3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, hydroxypivalicneopentyl glycol monoester, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis[4-(2-hydroxypropyl)-phenyl]propane, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, andalso polyethylene glycols, polypropylene glycols andpolytetrahydrofurans with molecular weights of in each case 200 to 10000. Apart from the homopolymers of ethylene oxide or propylene oxide,it is also possible to use block copolymers of ethylene oxide orpropylene oxide or copolymers which comprise ethylene oxide andpropylene oxide groups in incorporated form. Examples of parent alcoholswith more than two OH groups are trimethylolpropane, glycerol,pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol,triethoxycyanuric acid, sorbitan, sugars, such as sucrose, glucose,mannose. It is of course also possible to use the polyhydric alcoholsfollowing reaction with ethylene oxide or propylene oxide, in the formof the corresponding ethoxylates or propoxylates. The polyhydricalcohols can also firstly be converted into the corresponding glycidylethers by reaction with epichlorohydrin.

Further suitable crosslinkers f) are the vinyl esters or the esters ofmonohydric, unsaturated alcohols with ethylenically unsaturated C₃-C₆carboxylic acids, for example acrylic acid, methacrylic acid, itaconicacid, maleic acid or fumaric acid. Examples of such alcohols are allylalcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol,dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol,crotyl alcohol or cis-9-octadecen-1-ol. It is, however, also possible toesterify the monohydric, unsaturated alcohols with polybasic carboxylicacids, for example malonic acid, tartaric acid, trimellitic acid,phthalic acid, terephthalic acid, citric acid or succinic acid.

Further suitable crosslinkers f) are esters of unsaturated carboxylicacids with the above-described polyhydric alcohols, for example of oleicacid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Also suitable are straight-chain or branched, linear or cyclic aliphaticor aromatic hydrocarbons which have at least two double bonds, which, inthe case of the aliphatic hydrocarbons, must not be conjugated, e.g.divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene,4-vinyl-1-cyclohexene, trivinylcyclo-hexane or polybutadienes withmolecular weights of from 200 to 20 000.

Also suitable are amides of unsaturated carboxylic acids, such as, forexample, acrylic acid and methacrylic acid, itaconic acid, maleic acid,and N-allylamines of at least difunctional amines, such as, for example,1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine,diethylenetriamine or isophoronediamine. Likewise suitable are theamides of allylamine and unsaturated carboxylic acids, such as acrylicacid, methacrylic acid, itaconic acid, maleic acid, or at least dibasiccarboxylic acids, as have been described above.

Also suitable are triallylamine or corresponding ammonium salts, e.g.triallylmethylammonium chloride or methyl sulfate, as crosslinkers.

It is also possible to use N-vinyl compounds of urea derivatives, atleast difunctional amides, cyanurates or urethanes, for example of urea,ethyleneurea, propyleneurea or tartardiamide, e.g.N,N′-divinylethyleneurea or N,N′-divinylpropyleneurea.

Further suitable crosslinkers f) are divinyldioxane, tetraallylsilane ortetravinylsilane.

Particularly preferred crosslinkers are, for example,methylenebisacrylamide, divinylbenzene, triallylamine andtriallylammonium salts, divinylimidazole, N,N′-divinylethyleneurea,reaction products of polyhydric alcohols with acrylic acid ormethacrylic acid, methacrylic esters and acrylic esters of polyalkyleneoxides or polyhydric alcohols which have been reacted with ethyleneoxide and/or propylene oxide and/or epichlorohydrin, and also allyl orvinyl ethers of polyhydric alcohols, for example 1,2-ethanediol,1,4-butanediol, diethylene glycol, trimethylolpropane, glycerol,pentaerythritol, sorbitan and sugars, such as sucrose, glucose, mannose.

Particularly preferred crosslinkers f) are pentaerythritol triallylether, allyl ethers of sugars such as sucrose, glucose, mannose,divinylbenzene, N,N′-methylenebisacrylamide, N,N′-divinylethyleneurea,and (meth)acrylic esters of glycol, butanediol, trimethylolpropane orglycerol or (meth)acrylic esters of glycol reacted with ethylene oxideand/or epichlorohydrin, butanediol, trimethylolpropane or glycerol. Veryparticular preference is given to N,N′-methylenebisacrylamide,diallyltartardiamide, diallyl phthalate, diallylurea, glycoldi(meth)acrylate, allyl (meth)acrylate, and polyallyl ethers.

According to a suitable variant, the copolymerization for thepreparation of the ampholytic copolymers according to the inventiontakes place in the presence of at least one compound of component g)which is chosen from

-   g1) polyether-containing compounds,-   g2) polymers which have at least 50% by weight of repeat units    derived from vinyl alcohol,-   g3) cellulose, starch and derivatives thereof,    and mixtures thereof.

If the free-radical copolymerization of the components takes place inthe presence of at least one compound of component g), ampholyticcopolymers with advantageous properties are obtained. This can beattributed, for example, to the effect of component g) as protectivecolloid or emulsifier. This can, for example, also result from an atleast partial grafting onto component g) as graft base. However,mechanisms other than grafting are also conceivable. The copolymersaccording to the invention very generally include the process productsof free-radical-copolymerization, which is understood as meaning, forexample, pure graft polymers, mixtures of graft polymers with ungraftedcompounds of component g), copolymers of the abovementioned monomers,and any mixtures. Proportions of ungrafted compounds of component g) maybe advantageous depending on the intended use of the ampholyticcopolymers. Specific compounds g1) can, for example, have an effect asemulsifier or protective colloid.

Preferably, the amount of component g) used is 1 to 25% by weight,particularly preferably 3 to 20% by weight, based on the total weight ofthe components used for the polymerization.

Suitable polyether-containing compounds g1) are, for example,water-soluble or water-dispersible nonionic polymers which have alkyleneoxide repeat units. Preferably, the proportion of alkylene oxide repeatunits is at least 30% by weight, based on the total weight of thecompound g1). Suitable polyether-containing compounds g1) are, forexample, polyalkylene glycols, polyesters based on polyalkylene glycols,polyether-urethanes, and silicone derivatives containing polyalkyleneoxide groups.

Polyalkylene glycols suitable as component g1) generally have anumber-average molecular weight in the range from about 150 to 100 000,preferably 300 to 50 000, particularly preferably 500 to 40 000.Suitable polyalkylene glycols are, for example, polyethylene glycols,polypropylene glycols, polytetrahydrofurans and alkylene oxidecopolymers. Suitable alkylene oxides for the preparation of alkyleneoxide copolymers are, for example, ethylene oxide, propylene oxide,epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxidecopolymers can comprise, in copolymerized form, the alkylene oxide unitsin random distribution or in the form of blocks. Advantageously,homopolymers of ethylene oxide or copolymers which comprise ethyleneoxide are used. Preferably, the proportion of repeat units derived fromethylene oxide is 40 to 99% by weight. For example, copolymers ofethylene oxide and propylene oxide, copolymers of ethylene oxide andbutylene oxide, and also copolymers of ethylene oxide, propylene oxideand at least one butylene oxide are suitable. Also suitable as componentg1) are the allyl ethers of the abovementioned polyalkylene glycols.

Branched polyether-containing polymers g1) can be prepared by, forexample, adding at least one of the abovementioned alkylene oxides ontopolyalcohol radicals, e.g. onto pentaerythritol, glycerol or onto sugaralcohols, such as D-sorbitol and D-mannitol, or onto polysaccharides,such as cellulose and starch. The alkylene oxide units can be present inthe addition product in random distribution or in the form of blocks.

It is also possible to use polyesters of polyalkylene oxides andaliphatic or aromatic dicarboxylic acids, e.g. oxalic acid, succinicacid, adipic acid and terephthalic acid, as polyether-containingcompound g1). Suitable polyesters of polyalkylene oxides with molarmasses of from 1500 to 25 000 are described, for example, in EP-A-0 743962. Furthermore, it is also possible to use polycarbonates from thereaction of polyalkylene oxides with phosgene or with carbonates, suchas, for example, diphenyl carbonate, and also polyurethanes from thereaction of polyalkylene oxides with aliphatic and aromaticdiisocyanates as compound g1).

According to a preferred embodiment, a component g1) which includes atleast one polyether-urethane is used for the preparation of theampholytic copolymers.

Suitable polyether-urethanes are the condensation products of polyetherpolyols, such as polyetherdiols, with polyisocyanates, such asdiisocyanates. Suitable polyether polyols are the abovementionedpolyalkylene glycols which are obtainable, for example, from thepolymerization of cyclic ethers, such as tetrahydrofuran, or from thereaction of one or more alkylene oxides with a starter molecule whichhas two or more active hydrogen atoms.

Suitable polyisocyanates are chosen from compounds with 2 to 5isocyanate groups, isocyanate prepolymers with an average number of from2 to 5 isocyanate groups, and mixtures thereof. These include, forexample, aliphatic, cycloaliphatic and aromatic di-, tri- andpolyisocyanates. Suitable diisocyanates are, for example, tetramethylenediisocyanate, hexamethylene diisocyanate, 2,3,3-trimethylhexamethylenediisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate,1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate andisomer mixtures thereof (e.g. 80% 2,4- and 20% 2,6-isomer),1,5-naphthylene diisocyanate, 2,4- and 4,4′-diphenylmethanediisocyanate. A suitable triisocyanate is, for example, triphenylmethane4,4′,4″-triisocyanate. Also suitable are isocyanate prepolymers andpolyisocyanates which are obtainable by addition of the abovementionedisocyanates onto polyfunctional hydroxyl or amine group-containingcompounds. Also suitable are polyisocyanates which arise as a result ofbiuret or isocyanurate formation. Preference is given to usinghexamethylene diisocyanate, trimerized hexamethylene diisocyanate,isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, and mixtures thereof.

According to a further preferred embodiment, a component g1) whichincludes at least one polyalkylene oxide-containing silicone derivativeis used for the preparation of the ampholytic copolymers.

Suitable silicone derivatives g1) are the compounds known under the INCInames Dimethicone copolyols or silicone surfactants, such as, forexample, the compounds obtainable under the trade names Abil® (T.Goldschmidt), Alkasil® (Rhône-Poulenc), Silicone Polyol Copolymer®(Genesee), Belsil® (Wacker), Silwet® (OSI) or Dow Corning (Dow Corning).These include compounds with the CAS numbers 64365-23-7; 68937-54-2;68938-54-5; 68937-55-3.

Particularly suitable compounds g1) are those which comprise thefollowing structural elements:

-   R¹⁰ is an organic radical of 1 to 40 carbon atoms which can contain    amino, carboxylic acid or sulfonate groups or, when c=0 is also the    anion of an inorganic acid,    and where the radicals R⁵ may be identical or different, and either    originate from the group of aliphatic hydrocarbons having 1 to 20    carbon atoms, are cyclic aliphatic hydrocarbons having 3 to 20    carbon atoms, are of an aromatic nature or

and n is an integer from 1 to 6,

-   x and y are integers such that the molecular weight of the    polysiloxane block is between 300 and 30 000,-   a,b may be integers between 0 and 50, with the proviso that the sum    of a and b is greater than 0, and c is 0 or 1.

Preferred radicals R⁶ and R⁹ are those in which the sum of a+b isbetween 5 and 30.

Preferably, the groups R⁵ are chosen from the following group: methyl,ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl,dodecyl and octadecyl, cycloaliphatic radicals, specifically cyclohexyl,aromatic groups, specifically phenyl or naphthyl, mixedaromatic-aliphatic radicals, such as benzyl or phenylethyl, and alsotolyl and xylyl and R⁹.

Particularly suitable radicals R⁸ are those in which, whenR⁸=—(CO)_(c)—R¹⁰, R¹⁰ is any alkyl, cycloalkyl or aryl radical which hasbetween 1 and 40 carbon atoms and which can carry further ionogenicgroups such as NH₂, COOH, SO₃H.

Preferred inorganic radicals R¹⁰ are, when c=0, phosphate and sulfate.

Particularly preferred silicone derivatives e) are those of thestructure:

Suitable as graft base are preferably also polymers g2) which have atleast 50% by weight of vinyl alcohol units. Preferably, these polymerscomprise at least 70% by weight, very particularly preferably 80% byweight, of polyvinyl alcohol units. Such polymers are usually preparedby polymerization of a vinyl ester and subsequent at least partialalcoholysis, aminolysis or hydrolysis. Preference is given to vinylesters of linear and branched C₁-C₁₂-carboxylic acids, and veryparticular preference is given to vinyl acetate. The vinyl esters can ofcourse also be used in a mixture.

Suitable comonomers of the vinyl ester for the synthesis of the graftbase g2) are, for example, N-vinylcaprolactam, N-vinylpyrrolidone,N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole,3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methylsulfate, diallylammonium chloride, styrene, alkylstyrenes.

Further suitable comonomers for the preparation of the graft base g2)are, for example, monoethylenically unsaturated C₃-C₆-carboxylic acids,such as, for example, acrylic acid, methacrylic acid, crotonic acid,fumaric acid, and esters, amides and nitriles thereof, such as, forexample, methyl acrylate, ethyl acrylate, methyl methacrylate, ethylmethacrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxypropylacrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate,hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutylmethacrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate,diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,maleic anhydride and its half-ester, alkylene glycol (meth)acrylates,acrylamide, methacrylamide, N-dimethylacrylamide,N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers,such as, for example, methyl, ethyl, butyl or dodecyl vinyl ether,cationic monomers, such as dialkylaminoalkyl (meth)acrylates anddialkylaminoalkyl(meth)acrylamides, such as dimethylaminoethyl acrylate,diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and thesalts of the last-mentioned monomers with carboxylic acids or mineralacids, and also the quaternized products.

Preferred graft bases g2) are polymers which are prepared byhomopolymerization of vinyl acetate and subsequent at least partialhydrolysis, alcoholysis or aminolysis.

Particularly preferred graft bases g2) are polymers which are preparedby homopolymerization of vinyl acetate and subsequent at least partialsaponification. Polymers comprising such polyvinyl alcohol units areobtainable under the name Mowiol®.

As component g), preference is given to using cellulose, cellulosederivatives, starch and/or starch derivatives g3). These includesubstances which comprise saccharide structures. Such natural substancesare, for example, saccharides of vegetable or animal origin or productswhich are formed by metabolization by microorganisms, and degradationproducts thereof. Suitable graft bases g3) are, for example,oligosaccharides, polysaccharides, oxidatively, enzymatically orhydrolytically degraded polysaccharides, oxidatively hydrolyticallydegraded or oxidatively enzymatically degraded polysaccharides,chemically modified oligo- or polysaccharides and mixtures thereof.Preferred products are the compounds specified in U.S. Pat. No.5,334,287 in column 4, line 20 to column 5, line 45.

Suitable commercially available products are the C-Pur® and C-Dry®products from Cerestar.

If desired, mixtures of compounds of component g) can be used.

A preferred variant are ampholytic copolymers which are obtainable bycopolymerization in the presence of at least one compound g1) which ischosen from polyalkylene oxides, polyalkylene oxide-containing siliconederivatives and mixtures thereof.

Preferably, the copolymers according to the invention have a K value(measured in accordance with E. Fikentscher, Cellulose-Chemie 13 (1932),pp. 58-64) on a 1% strength by weight solution in water in the rangefrom about 30 to 300, particularly preferably 40 to 150.

Depending on the K value, the polymers according to the invention aresuitable for a large number of cosmetic and pharmaceutical applications.For example, polymers with a K value up to about 50 can advantageouslybe formulated as sprays (aerosol sprays and pump sprays). Polymers witha K value in a range from about 50 to 90 are advantageously suitable forgels and foams. For shampoos and skin cosmetic applications, polymerswith a K value of at least 80 are preferably suitable.

The ampholytic copolymers according to the invention are preferablyobtainable by free-radical copolymerization of

-   -   0.1 to 30% by weight, preferably 0.3 to 25% by weight, based on        the total weight of the components used for the polymerization,        of at least one component a),    -   0.1 to 40% by weight, based on the total weight of the        components used for the polymerization, of at least one        component b),    -   40 to 99.8% by weight, based on the total weight of the        components used for the polymerization, of at least one        component c),    -   0 to 20% by weight of at least one further monomer d),    -   0 to 10% by weight, preferably 0.1 to 7% by weight, of at least        one polyether acrylate e),    -   0 to 10% by weight, preferably 0 to 5% by weight, of at least        one crosslinker f),        optionally in the presence of up to 25% by weight, based on the        total weight of the components used for the polymerization, of        at least one component g).

Particular preference is given to ampholytic copolymers obtainable byfree-radical copolymerization of

-   -   0.1 to 25% by weight, preferably 0.3 to 20% by weight, based on        the total weight of the components used for the polymerization,        of at least one monomer which is chosen from acrylic acid,        methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid,        styrene-4-sulfonic acid and mixtures thereof,    -   1 to 20% by weight, based on the total weight of the components        used for the polymerization, of at least one compound b) which        is chosen from N,N-dimethylaminopropyl (meth)acrylate,        vinylimidazole and mixtures thereof,    -   60 to 98.9% by weight, based on the total weight of the        components used for the polymerization, of at least one        compound c) which is chosen from acrylamide, methacrylamide,        N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide and        mixtures thereof.

Furthermore, particular preference is given to the ampholytic copolymerobtainable by free-radical polymerization of

-   -   5 to 20% by weight, based on the total weight of the components        used for the polymerization, of at least one monomer which is        chosen from acrylic acid, methacrylic acid,        2-acrylamido-2-methylpropanesulfonic acid, stryene-4-sulfonic        acid and mixtures thereof,    -   10 to 30% by weight, based on the total weight of the components        used for the polymerization, of at least one compound b) which        is chosen from N,N-dimethylaminopropyl (meth)acrylate,        vinylimidazole and mixtures thereof,    -   50 to 85% by weight, based on the total weight of the components        used for the polymerization, of at least one compound c) which        is chosen from acrylamide, methacrylamide, N-vinylpyrrolidone,        N-vinylcaprolactam, N-vinylformamide and mixtures thereof,    -   0 to 25% by weight of at least one further monomer d),    -   0 to 10% by weight, preferably 0.1 to 7% by weight, of at least        one polyether acrylate e).

The abovementioned particularly preferred copolymers can additionallycomprise, in copolymerized form, 0.05 to 1% by weight of at least onecrosslinker f). This is, in particular, methyl bisacrylamide and/orN,N′-diallyltartardiamide.

The abovementioned particularly preferred copolymers can additionallycomprise, in copolymerized form, 1 to 10% by weight of at least oneester of an α,β-ethylenically unsaturated mono- or dicarboxylic acidwith a C₁-C₃₀-alkanol, preferably stearyl (meth)acrylate.

According to a specific embodiment, the abovementioned particularlypreferred copolymers are obtainable by copolymerization in the presenceof up to 10% by weight, based on the total weight of the components usedfor the polymerization, of at least one component g).

A preferred embodiment provides copolymers which consist of repeat unitsof

-   -   vinylpyrrolidone,    -   acrylic acid and/or methacrylic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   2-acrylamido-2-methylpropeanesulfonic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   acrylamide and/or methacrylamide,    -   acrylic acid and/or methacrylic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   acrylamide and/or methacrylamide,    -   2-acrylamido-2-methylpropanesulfonic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   acrylic acid and/or methacrylic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate,    -   at least one monomer of the formula        CH₂═CR^(c)—C(═O)—O—R^(d)    -   in which    -   R^(c) is H or methyl and    -   R^(d) is linear C₁-C₄-alkyl.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   2-acrylamido-2-methylpropanesulfonic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate,    -   at least one monomer of the formula        CH₂═CR^(c)—C(═O)—O—R^(d)    -   in which    -   R^(c) is H or methyl and    -   R^(d) is linear C₁-C₄-alkyl.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   acrylamide and/or methacrylamide,    -   acrylic acid and/or methacrylic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate,    -   at least one monomer of the formula        CH₂═CR^(c)—C(═O)—O—R^(d)    -   in which    -   R^(c) is H or methyl and    -   R^(d) is linear C₁-C₄-alkyl.

A further preferred embodiment provides copolymers which consist ofrepeat units of

-   -   vinylpyrrolidone,    -   acrylamide and/or methacrylamide,    -   2-acrylamido-2-methylpropanesulfonic acid,    -   dimethylaminoethyl methacrylate or        dimethylaminopropylmethacrylamide or vinylimidazole or        tert-butylaminoethyl methacrylate and    -   at least one polyether acrylate,    -   at least one monomer of the formula        CH₂═CR^(c)—C(═O)—O—R^(d)    -   in which    -   R^(c) is H or methyl and    -   R^(d) is linear C₁-C₄-alkyl.

The copolymers of the abovementioned preferred embodiments preferablyadditionally comprise a salt of 2-acrylamido-2-methylpropanesulfonicacid, preferably the sodium salt, in copolymerized form.

The copolymers of the abovementioned preferred embodiments preferablyadditionally comprise a quaternized monomer containing amine groups,preferably quaternized vinylimidazole, in copolymerized form.

The copolymers of the abovementioned preferred embodiments preferablyadditionally comprise up to 1% by weight, based on the total weight ofthe monomers used for the polymerization, of at least one crosslinker incopolymerized form.

The ampholytic copolymers are prepared in accordance with customaryprocesses known to the person skilled in the art, preferably by solutionpolymerization and precipitation polymerization.

Preferred solvents for solution polymerization are aqueous solvents,such as water and mixtures of water with water-miscible solvents, forexample alcohols, such as methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, andglycols, such as ethylene glycol, propylene glycol and butylene glycol,and the methyl or ethyl ethers of dihydric alcohols, diethylene glycol,triethylene glycol, polyethylene glycols with number-average molecularweights up to about 3 000, glycerol and dioxane. Particular preferenceis given to polymerization in water or a water/alcohol mixture, forexample a water/ethanol mixture.

The precipitation polymerization takes place, for example, in an ester,such as ethyl acetate or butyl acetate as solvent. The resulting polymerparticles precipitate out of the reaction solution and can be isolatedby customary methods, such as filtration by means of subatmosphericpressure. In the case of precipitation polymerization, the polymersobtained usually have higher molecular weights than in the case ofsolution polymerization.

The polymerization temperatures are preferably in a range from about 30to 120° C., particularly preferably 40 to 100° C. The polymerizationusually takes place under atmospheric pressure, although it can alsotake place under reduced or increased pressure. A suitable pressurerange is between 1 and 5 bar.

To prepare the polymers, the monomers, optionally in the presence ofcomponent e), can be polymerized using initiators which form freeradicals.

Initiators which can be used for the free-radical polymerization are theperoxo and/or azo compounds customary for this purpose, for examplealkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoylperoxide, succinyl peroxide, di-tert-butyl peroxide, tert-butylperbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate,tert-butyl permaleate, cumene hydroperoxide, diisopropylperoxydicarbamate, bis(o-toloyl) peroxide, didecanoyl peroxide,dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate,tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide,azobisisobutyronitrile, azobis(2-amidinopropane) dihydrochloride or2-2′-azobis(2-methylbutyronitrile). Also suitable are initiator mixturesor redox initiator systems, such as, for example, ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite, tert-butyl hydroperoxide/sodium hydroxymethane-sulfinate,H₂O₂/Cu¹.

To adjust the molecular weight, the polymerization can take place in thepresence of at least one regulator. Regulators which can be used are thecustomary compounds known to the person skilled in the art, such as, forexample, sulfur compounds, e.g. mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid or dodecylmercaptan, and alsotribromochloromethane or other compounds which have a regulating effecton the molecular weight of the resulting polymers. A preferred regulatoris cysteine.

To achieve the purest possible polymers with a low residual monomercontent, the polymerization (main polymerization) can be followed by anafterpolymerization step. The afterpolymerization can take place in thepresence of the same initiator system as or a different initiator systemto the main polymerization. Preferably, the afterpolymerization takesplace at least at the same, preferably at a higher, temperature than themain polymerization. The temperature in the main polymerization and theafterpolymerization is preferably at most 90° C. Preferably, thereaction batch is subjected to a stripping with steam or a steamdistillation.

If an organic solvent is used in the preparation of the polymers, thenthis can be removed by customary processes known to the person skilledin the art, e.g. by distillation at reduced pressure.

As described at the outset, the polymerization preferably takes place ata pH in the range from 5.5 to 8.0, particularly preferably from 5.6 to7.5 and especially from 5.8 to 7.3. This generally leads to theattainment of the purest possible polymers with a low residual monomercontent, which may be attributed to the fact that amines which areformed as cleavage product and which can in some circumstances reactwith some monomers to give undesired secondary products under thepolymerization conditions are removed. The pH is adjusted, as likewisedescribed at the outset, by adding a suitable acid or by adding asuitable base.

Products with particularly high purity and correspondingly advantageousproperties for use in cosmetics can be achieved if the reaction productis subjected to a steam distillation or a stripping with steam followingthe polymerization, optionally before and/or after anafterpolymerization. This treatment with steam also serves, for example,to remove amines and further undesired secondary products which can beremoved with steam from the reaction mixture. Preferably, the steamtreatment takes place at least between the main polymerization andafterpolymerization. The pH of the polymerization product is preferablyadjusted to a value of at most 6.5 prior to the steam treatment. Thetemperature of the steam used and of the treated polymer solution ispreferably at least 90° C.

The polymer solutions can be converted into powder form by variousdrying processes, such as, for example, spray drying, fluidized spraydrying, roller drying or freeze drying. Preference is given to usingspray drying. The resulting dry polymer powders can advantageously beconverted again into an aqueous solution or dispersion by dissolution orredispersion in water. Pulverulent copolymers have the advantage ofbetter storability, ability to be transported more easily and generallyexhibit a lower tendency toward microbial attack.

The anionogenic groups (acid groups) of the polymers can be partially orcompletely neutralized with a base. The bases used for theneutralization of the polymers may be alkali metal bases, such as sodiumhydroxide solution, potassium hydroxide solution, soda, sodium hydrogencarbonate, potassium carbonate or potassium hydrogen carbonate andalkaline earth metal bases, such as calcium hydroxide, calcium oxide,magnesium hydroxide or magnesium carbonate, and also amines. Suitableamines are, for example, C₁-C₆-alkylamines, preferably n-propylamine andn-butylamine, dialkylamines, preferably diethylpropylamine anddipropylmethylamine, trialkylamines, preferably triethylamine andtriisopropylamine. Preference is given to aminoalcohols, e.g.trialkanolamines such as triethanolamine, alkyldialkanolamines, such asmethyl- or ethyldiethanolamine, and dialkylalkanolamines, such asdimethylethanolamine, and 2-amino-2-methyl-1-propanol. Particularly foruse in hair-treatment compositions, NaOH, KOH,2-amino-2-methyl-1-propanol, 2-amino-2-ethylpropane-1,3-diol,diethylaminopropylamine and triisopropanolamine have proven successfulfor the neutralization of the polymers containing acid groups. Theneutralization of the acid groups can also be carried out using mixturesof two or more bases, e.g. mixtures of sodium hydroxide solution andtriisopropanolamine. The neutralization can take place partially orcompletely depending on the intended use.

Charged cationic groups can be produced from the present cationogenicnitrogen-containing groups either by protonation, e.g. with mono- orpolybasic carboxylic acids, such as lactic acid or tartaric acid, orwith mineral acids, such as phosphoric acid, sulfuric acid andhydrochloric acid, or by quaternization, e.g. with alkylating agents,such as C₁- to C₄-alkyl halides or sulfates. Examples of alkylatingagents are ethyl chloride, ethyl bromide, methyl chloride, methylbromide, dimethyl sulfate and diethyl sulfate.

As a rule, a neutralization takes place such that the pH of a 0.1 molaraqueous solution of the water-soluble ampholytic copolymers according tothe invention at a temperature of 20° C. is in a range from 5.5 to 8.0,particularly preferably from 5.6 to 7.5 and in particular from 5.8 to7.3.

The invention further provides polyelectrolyte complexes which compriseat least one ampholytic copolymer, as defined above, and at least onefurther poly-electrolyte different therefrom.

Suitable further polyelectrolytes are in principle chosen from polymerswith anionogenic and/or anionic groups, polymers which cationogenicand/or cationic groups, ampholytic copolymers and mixtures thereof.

The polyelectrolyte complexes preferably comprise at least oneampholytic copolymer according to the invention and at least one furtherpolyelectrolyte different therefrom in a weight ratio of from about 10:1to 1:10. Preferably, in the polyelectrolyte complexes according to theinvention, the molar ratio of anionogenic and anionic groups tocationogenic and cationic groups is about 0.8:1 to 1:0.8, preferably0.9:1 to 1:0.9.

Anionic polymers suitable as polyelectrolytes are, for example,homopolymers and copolymers of acrylic acid and methacrylic acid andsalts thereof. These also include crosslinked polymers of acrylic acid,as are available under the INCI name Carbomer. Such crosslinkedhomopolymers of acrylic acid are, for example, commercially availableunder the name Carbopol® from Noveon (formerly BF GOODRICH). Preferenceis also given to hydrophobically modified crosslinked polyacrylatepolymers, such as Carbopol® Ultrez 21 from Noveon. Polyelectrolytecomplexes according to the invention based on homopolymers andcopolymers of acrylic acid and methacrylic acid are suitable inadvantageous manner for formulation as gels, for example for settinggels, and for the formulation of foams.

Examples of suitable anionic polymers are also acid-modified starches.Acid-modified starches and process for their preparation are known inprinciple to the person skilled in the art and are described, forexample, in Ullmann's Encyclopedia of Industrial Chemistry, 5^(th)edition on CD-ROM, Starch and other Polysaccharides, 1.2.2.1, Wiley-VCH(1997). Polyelectrolyte complexes based on anionically modified starchesare suitable in an advantageous manner for formulating gels and for useas conditioner for shampoos.

Further examples of suitable anionic polymers are copolymers of acrylicacid and acrylamide and salts thereof; sodium salts ofpolyhydroxycarboxylic acids, water-soluble or water-dispersiblepolyesters, polyurethanes and polyureas. Particularly suitable polymersare copolymers of (meth)acrylic acid and polyether acrylates, where thepolyether chain is terminated by a C₈-C₃₀-alkyl radical. These include,for example, acrylate/beheneth-25-methacrylate copolymers, which areavailable under the name Aculyn® from Rohm and Haas. Particularlysuitable polymers are furthermore copolymers of t-butyl acrylate, ethylacrylate, methacrylic acid (e.g. Luvimer® 100P), copolymers of ethylacrylate and methacrylic acid (e.g. Luvimer® MAE and Luviflex® soft),copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid(Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid andoptionally further vinyl esters (e.g. Luviset® grades), maleic anhydridecopolymers, optionally reacted with alcohol, anionic polysiloxanes, e.g.carboxyfunctional, t-butyl acrylate, methacrylic acid (e.g. Luviskol®VBM), copolymers of acrylic acid and methacrylic acid with hydrophobicmonomers, such as, for example, C₄-C₃₀-alkyl esters of meth(acrylicacid), C₄-C₃₀-alkyl vinyl esters, C₄-C₃₀-alkyl vinyl ethers andhyaluronic acid. Examples of anionic polymers are also vinylacetate/crotonic acid copolymers, as are available commercially, forexample, under the names Resyn® (National Starch) and Gafset® (GAF), andvinylpyrrolidone/vinyl acrylate copolymers, obtainable, for example,under the trade name Luviflex® (BASF). Other suitable polymers are thevinylpyrrolidone/acrylate terpolymer available under the name Luviflex®VBM-35 (BASF), and sodium sulfonate-containing polyamides or sodiumsulfonate-containing polyesters.

Further suitable polymers are cationic polymers with the INCI namePolyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazoliumsalts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care),copolymers of N-vinylpyrrolidone/dimethylaminoethyl methacrylate,quaternized with diethylsulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and-10), acrylamido copolymers (Polyquaternium-7) and chitosan. Suitablecationic (quaternized) polymers are also Merquat® (polymer based ondimethyldiallylammonium chloride), Gafquat® (quaternary polymers whichare formed by the reaction of polyvinylpyrrolidone with quaternaryammonium compounds), Polymer JR (hydroxyethylcellulose with cationicgroups) and vegetable-based cationic polymers, e.g. guar polymers, suchas the Jaguar® grades from Rhodia. Also suitable are the polymers with(meth)acrylamide units described in German patent application P 102 43573.1. In addition, the polymers described in the German patentapplication P 103 31 870.4, which contain vinylimidazole and/or aderivative thereof in copolymerized form, are also suitable.

Suitable polymers are also amphoteric or zwitterionic polymers, such asthe octylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxy-propyl methacrylate copolymers obtainable underthe names Amphomer® (National Starch), and zwitterionic polymers as aredisclosed for example, in the German patent applications DE 39 29 973,DE 21 50 557, DE 28 17 369 and DE 37 08 451.Acrylamidopropyltrimethylammonium chloride/acrylic acid or methacrylicacid copolymers and the alkali metal and ammonium salts thereof arepreferred zwitterionic polymers. Other suitable zwitterionic polymersare methacroylethylbetaine/methacrylate copolymers, which are availablecommercially under the name Amersette® (AMERCHOL), and copolymers ofhydroxyethyl methacrylate, methyl methacrylate, N,N-dimethylaminoethylmethacrylate and acrylic acid (Jordapon®).

The invention further provides a cosmetic or pharmaceutical compositioncomprising

-   A) at least one ampholytic copolymer, as defined above, or a    polyelectrolyte complex, as defined above, and-   B) at least one cosmetically acceptable carrier.

The cosmetically acceptable carrier B) is preferably chosen from

-   i) water,-   ii) water-miscible organic solvents, preferably C₁-C₄-alkanoles,-   iii) oils, fats, waxes,-   iv) esters of C₆-C₃₀-monocarboxylic acids with mono-, di- or    trihydric alcohols different from iii),-   v) saturated acyclic and cyclic hydrocarbons,-   vi) fatty acids,-   vii) fatty alcohols    and mixtures thereof.

The compositions according to the invention have, for example, an oil orfatty component B) which is chosen from: hydrocarbons of low polarity,such as mineral oils; linear saturated hydrocarbons, preferably withmore than 8 carbon atoms, such as tetradecane, hexadecane, octadecaneetc.; cyclic hydrocarbons, such as decahydronaphthalene; branchedhydrocarbons; animal and vegetable oils; waxes; wax esters; vaseline;esters, preferably esters of fatty acids, such as, for example, theesters of C₁-C₂₄-monoalcohols with C₁-C₂₂-monocarboxylic acids, such asisopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propylpalmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanylpalmitate, triacontanyl palmitate, dotriacontanyl palmitate,tetratriacontanyl palmitate, hexacosanyl stearate, octacosanyl stearate,triacontanyl stearate, dotriacontanyl stearate, tetratriacontanylstearate; salicylates, such as C₁-C₁₀-salicylates, e.g. octylsalicylate; benzoate esters, such as C₁₀-C₁₅-alkyl benzoates, benzylbenzoate; other cosmetic esters, such as fatty acid triglycerides,propylene glycol monolaurate, polyethylene glycol monolaurate,C₁₀-C₁₅-alkyl lactates, etc. and mixtures thereof.

Suitable silicone oils B) are, for example, linearpolydimethylsiloxanes, poly(methylphenylsiloxanes), cyclic siloxanes andmixtures thereof. The number-average molecular weight of thepolydimethylsiloxanes and poly(methylphenylsiloxanes) is preferably in arange from about 1000 to 150 000 g/mol. Preferred cyclic siloxanes have4- to 8-membered rings. Suitable cyclic siloxanes are commerciallyavailable, for example under the name cyclomethicone.

Preferred oil or fatty components B) are chosen from paraffin andparaffin oils; vaseline; natural fats and oils, such as castor oil,soybean oil, groundnut oil, olive oil, sunflower oil, sesame oil,avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil,cod-liver oil, pork lard, spermaceti, spermaceti oil, sperm oil,wheatgerm oil, macadamia nut oil, evening primrose oil, jojoba oil;fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol,stearyl alcohol, oleyl alcohol, cetyl alcohol; fatty acids, such asmyristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid,linolenic acid and saturated, unsaturated and substituted fatty acidsdifferent therefrom; waxes, such as beeswax, carnauba wax, candilillawax, spermaceti, and mixtures of the abovementioned oil or fattycomponents.

Suitable cosmetically and pharmaceutically compatible oil or fattycomponents B) are described in Karl-Heinz Schrader, Grundlagen undRezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics],2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which referenceis hereby made.

Suitable hydrophilic carriers B) are chosen from water, mono-, di- orpolyhydric alcohols having preferably 1 to 8 carbon atoms, such asethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol,etc.

The cosmetic compositions according to the invention may be skincosmetic, dermatological or hair cosmetic compositions.

Preferably, the compositions according to the invention are used in theform of a gel, foam, spray, an ointment, cream, emulsion, suspension,lotion, milk or paste. If desired, liposomes or microspheres can also beused.

The cosmetically or pharmaceutically active compositions according tothe invention can additionally comprise cosmetically and/ordermatologically active ingredients and auxiliaries.

Preferably, the cosmetic compositions according to the inventioncomprise at least one ampholytic copolymer as defined above or apolyelectrolyte complex A, at least one carrier B as defined above andat least one constituent different from component A which is chosen fromcosmetically active ingredients, emulsifiers, surfactants,preservatives, perfume oils, thickeners, hair polymers, hair and skinconditioners, branched polymers, crosslinked polymers, graft polymers,water-soluble or dispersible silicone-containing polymers, lightprotection agents, bleaches, gel formers, care agents, colorants, tints,tanning agents, dyes, pigments, bodying agents, moisturizers, refattingagents, collagen, protein hydrolysates, lipids, antioxidants, antifoams,antistats, emollients, softeners.

Suitable cosmetically and/or dermatologically active ingredients are,for example, coloring active ingredients, skin and hair pigmentationagents, tinting agents, tanning agents, bleaches, keratin-hardeningsubstances, antimicrobial active ingredients, light filter activeingredients, repellent active ingredients, substances with hyperemicactivity, substances with keratolytic and keratoplastic activity,anti-dandruff active ingredients, antiphlogistics, substances which havea keratinizing effect, substances which act as antioxidants or asfree-radical scavengers, skin moisturizers or moisturizers, refattingactive ingredients, antierythematous or anti-allergic active ingredientsand mixtures thereof.

Artificially skin-tanning active ingredients which are suitable fortanning the skin without natural or artificial irradiation with UV raysare, for example, dihydroxyacetone, alloxan and walnut shell extract.Suitable keratin-hardening substances are usually active ingredients asare also used in antiperspirants, such as, for example, potassiumaluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.Antimicrobial active ingredients are used in order to destroymicroorganisms or to inhibit their growth and thus serve both aspreservatives and also as a deodorizing substance which reduces theformation or the intensity of body odor. These include, for example,customary preservatives known to the person skilled in the art, such asp-hydroxybenzoates, imidazolidinylurea, formaldehyde, sorbic acid,benzoic acid, salicylic acid, etc. Advantageous preservatives are, forexample, paraben esters, such as methylparaben, ethylparaben,propylparaben, etc. A suitable mixture of paraben esters inphenoxyethanol is commercially available under the name Phenonip®(Clairant). Also suitable are chlorinated and nonchlorinatedisothiazolones. These are available, for example, under the name Euxyl®K 100 (Schülke & Mayr). Such deodorizing substances are, for example,zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethylcitrate, chlorhexidine etc. Suitable light filter active ingredients aresubstances which absorb UV rays in the UV-B and/or UV-A region. SuitableUV filters are, for example, 2,4,6-triaryl-1,3,5-triazines in which thearyl groups may each carry at least one substituent which is preferablychosen from hydroxyl, alkoxy, specifically methoxy, alkoxycarbonyl,specifically methoxycarbonyl and ethoxycarbonyl and mixtures thereof.Also suitable are p-aminobenzoates, cinnamates, benzophenones, camphorderivatives, and pigments which stop UV rays, such as titanium dioxide,talc and zinc oxide. Suitable repellent active ingredients are compoundswhich are able to drive away or repel certain animals, in particularinsects, from humans. These include, for example,2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide etc. Suitable substanceswith hyperemic activity which stimulate blood flow through the skin are,for example, ethereal oils, such as dwarf pine, lavender, rosemary,juniper berry, horsechestnut extract, birch leaf extract, hayseedextract, ethyl acetate, camphor, menthol, peppermint oil, rosemaryextract, eucalyptus oil, etc. Suitable keratolytic and keratoplasticsubstances are, for example, salicylic acid, potassium thioglycolate,thioglycolic acid and salts thereof, sulfur, etc. Suitable antidandruffactive ingredients are, for example, sulfur, sulfur polyethylene glycolsorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione,aluminum pyrithione, etc. Suitable antiphlogistics which counter skinirritations are, for example, allantoin, bisabolol, Dragosantol,chamomile extract, panthenol, etc.

The cosmetic compositions according to the invention can comprise, ascosmetic and/or pharmaceutical active ingredient (and also optionally asauxiliary), at least one cosmetically or pharmaceutically acceptablepolymer different from compounds of component A). These include verygenerally polymers which have no anionogenic, anionic, cationogenic orcationic groups on the polymer backbone.

These include neutral polymers, such as polyvinylpyrrolidones,copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinylpropionate, polysiloxanes, polyvinylcaprolactam and other copolymerswith N-vinylpyrrolidone, polyethyleneimines and salts thereof,polyvinylamines and salts thereof, cellulose derivatives, polyasparticacid salts and derivatives. These include, for example, Luviflex® Swing(partially saponified copolymer of polyvinyl acetate and polyethyleneglycol, BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersiblepolymers or oligomers, such as polyvinylcaprolactam, e.g. Luviskol® Plus(BASF), or polyvinylpyrrolidone and copolymers thereof, in particularwith vinyl esters, such as vinyl acetate, e.g. Luviskol® VA 37 (BASF);polyamides, e.g. those based on itaconic acid and aliphatic diamines, asare described, for example, in DE-A-43 33 238.

Suitable polymers are also nonionic, siloxane-containing, water-solubleor -dispersible polymers, e.g. polyether siloxanes, such as Tegopren®(Goldschmidt) or Belsil® (Wacker).

The formulation base of pharmaceutical compositions according to theinvention preferably comprises pharmaceutically acceptable auxiliaries.Pharmaceutically acceptable auxiliaries are the auxiliaries which areknown for use in the fields of pharmacy, food technology and relatedfields, in particular the auxiliaries listed in the relevantpharmacopoeia (e.g. DAB Ph. Eur. BP NF), and other auxiliaries whoseproperties do not preclude a physiological application.

Suitable auxiliaries may be: lubricants, wetting agents, emulsifying andsuspending agents, preservatives, antioxidants, antiirritativesubstances, chelating agents, emulsion stabilizers, film formers, gelformers, odor-masking agents, resins, hydrocolloids, solvents,solubility promoters, neutralizing agents, permeation accelerators,pigments, quaternary ammonium compounds, refatting and superfattingagents, ointment bases, cream bases or oil bases, silicone derivatives,stabilizers, sterilizing agents, propellants, drying agents, opacifiers,thickeners, waxes, softeners, white oils. Formulation in this regard isbased on expert knowledge, as given, for example, in Fiedler, H. P.Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete[Lexicon of auxiliaries for pharmacy, cosmetics and related fields], 4thEd., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.

To prepare the dermatological compositions according to the invention,the active ingredients can be mixed or diluted with a suitable auxiliary(excipient). Excipients can be solid, semisolid or liquid materialswhich can serve as vehicle, carrier or medium for the active ingredient.The admixing of further auxiliaries is carried out, where desired, inthe manner known to the person skilled in the art.

In a first preferred embodiment, the compositions according to theinvention are skin-cleansing compositions.

Preferred skin-cleansing compositions are soaps of liquid to gel-likeconsistency, such as transparent soaps, luxury soaps, deodorant soaps,cream soaps, baby soaps, skin protection soaps, abrasive soaps andsyndets, pasty soaps, soft soaps and washing pastes, liquid washing,shower and bath preparations, such as washing lotions, shower baths andshower gels, foam baths, oil baths and scrub preparations.

According to a further preferred embodiment, the compositions accordingto the invention are cosmetic compositions for the care and protectionof the skin, nail care compositions or preparations for decorativecosmetics.

Particular preference is given to skincare compositions, personalhygiene compositions, foot care compositions, light protectioncompositions, repellents, shaving compositions, depilatory compositions,antiacne compositions, make-up, mascara, lipsticks, eye shadows, kohlpencils, eyeliners, blushers and eyebrow pencils.

The skincare compositions according to the invention are, in particular,W/O or O/W skin creams, day creams and night creams, eye creams, facecreams, antiwrinkle creams, moisturizing creams, bleaching creams,vitamin creams, skin lotions, care lotions and moisturizing lotions.

Skin cosmetic and dermatological compositions based on theabovedescribed polymers or polyelectrolytes A) exhibit advantageouseffects. The polymers can, inter alia, contribute to the moisturizingand conditioning of the skin and to an improvement in the feel of theskin. The polymers can also act as thickeners in the formulations. Byadding the polymers according to the invention, it is possible toachieve a considerable improvement in skin compatibility in certainformulations.

Skin cosmetic and dermatological compositions preferably comprise atleast one ampholytic copolymer or a polyelectrolyte complex A) in anamount of from about 0.001 to 30% by weight, preferably 0.01 to 20% byweight, very particularly preferably 0.1 to 12% by weight, based on thetotal weight of the composition.

Light protection agents based on component A), in particular, have theproperty of increasing the residence time of the UV-absorbingingredients compared with customary auxiliaries such aspolyvinylpyrrolidone.

Depending on the field of use, the compositions according to theinvention can be applied in a form suitable for skin care, such as, forexample, as cream, foam, gel, pencil, mousse, milk, spray (pump spray orspray containing propellant) or lotion.

As well as comprising the ampholytic copolymers or polyelectrolytecomplexes A) and suitable carriers, the skin cosmetic preparations canalso comprise further active ingredients and auxiliaries customary inskin cosmetics, as described above. These include, preferably,emulsifiers, preservatives, perfume oils, cosmetic active ingredients,such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol,light protection agents, bleaches, colorants, tinting agents, tanningagents, collagen, protein hydrolysates, stabilizers, pH regulators,dyes, salts, thickeners, gel formers, bodying agents, silicones,moisturizers, refatting agents and further customary additives.

Preferred oil and fatty components of the skin cosmetic anddermatological compositions are the abovementioned mineral and syntheticoils, such as, for example, paraffins, silicone oils and aliphatichydrocarbons having more than 8 carbon atoms, animal and vegetable oils,such as, for example, sunflower oil, coconut oil, avocado oil, oliveoil, lanolin, or waxes, fatty acids, fatty acid esters, such as, forexample, triglycerides of C₆-C₃₀-fatty acids, wax esters, such as, forexample, jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin andacetylated lanolin, and mixtures thereof.

The polymers according to the invention can also be mixed withtraditional polymers where specific properties are to be set.

To set certain properties, such as, for example, improving the feel tothe touch, the spreading behavior, the water resistance and/or thebinding of active ingredients and auxiliaries, such as pigments, theskin cosmetic and dermatological preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkyl siloxanes, polyarylsiloxanes, polyarylalkyl siloxanes, polyether siloxanes or siliconeresins.

The cosmetic or dermatological preparations are prepared by customarymethods known to the person skilled in the art.

The cosmetic and dermatological compositions are preferably in the formof emulsions, in particular water-in-oil (W/O) emulsions or oil-in-water(O/W) emulsions. It is, however, also possible to choose other types offormulations, for example hydrodispersions, gels, oils, oleogels,multiple emulsions, for example in the form of W/O/W or O/W/O emulsions,anhydrous ointments or ointment bases, etc.

The emulsions are prepared by known methods. Apart from the ampholyticcopolymer or polyelectrolyte complex A), the emulsions usually comprisecustomary constituents, such as fatty alcohols, fatty acid esters and,in particular, fatty acid triglycerides, fatty acids, lanolin andderivatives thereof, natural or synthetic oils or waxes and emulsifiersin the presence of water. The choice of emulsion type-specific additivesand the preparation of suitable emulsions is described, for example, inSchrader, Grundlagen und Rezepturen der Kosmetika [Fundamentals andFormulations of Cosmetics], Hüthig Buch Verlag, Heidelberg, 2nd Edition,1989, third part, to which express reference is made here.

A suitable emulsion, e.g. for a skin cream etc., generally comprises anaqueous phase which is emulsified by means of a suitable emulsifiersystem in an oil or fatty phase.

The proportion of the emulsifier system in this type of emulsion ispreferably about 4 and 35% by weight, based on the total weight of theemulsion. The proportion of the fatty phase is preferably about 20 to60% by weight. The proportion of the aqueous phase is preferably about20 and 70%, in each case based on the total weight of the emulsion. Theemulsifiers are those customarily used in this type of emulsion. Theyare chosen, for example, from: C₁₂-C₁₈-sorbitan fatty acid esters;esters of hydroxystearic acid and C₁₂-C₃₀-fatty alcohols; mono- anddiesters of C₁₂-C₁₈-fatty acids and glycerol or polyglycerol;condensates of ethylene oxide and propylene glycols;oxypropylenated/oxyethylated C₁₂-C₁₈-fatty alcohols; polycyclicalcohols, such as sterols; aliphatic alcohols with a high molecularweight, such as lanolin; mixtures of oxypropylenated/polyglycerolatedalcohols and magnesium isostearate; succinic esters ofpolyoxyethylenated or polyoxypropylenated fatty alcohols; and mixturesof magnesium lanolate, calcium lanolate, lithium lanolate, zinc lanolateor aluminum lanolate and hydrogenated lanolin or lanolin alcohol.

Preferred fatty components which may be present in the fatty phase ofthe emulsions are: hydrocarbon oils, such as paraffin oil, purcellinoil, perhydrosqualene and solutions of microcrystalline waxes in theseoils; animal or vegetable oils, such as sweet almond oil, avocado oil,calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil,olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whosedistillation start-point under atmospheric pressure is about 250° C. andwhose distillation end-point is 410° C., such as, for example, vaselineoil; esters of saturated or unsaturated fatty acids, such as alkylmyristates, e.g. i-propyl, butyl or cetyl myristate, hexadecyl stearate,ethyl or i-propyl palmitate, octanoic or decanoic acid triglycerides andcetyl ricinoleate.

The fatty phase may also comprise silicone oils soluble in other oils,such as dimethylpolysiloxane, methylphenylpolysiloxane and the siliconeglycol copolymer, fatty acids and fatty alcohols.

In order to favor the retention of oils, in addition to the ampholyticcopolymers or polyelectrolyte complexes A), it is also possible to usewaxes, such as, for example, carnauba wax, candililla wax, beeswax,microcrystalline wax, ozokerite wax and the oleates, myristates,linoleates and stearates of Ca, Mg and Al.

The water-in-oil emulsions are generally prepared by introducing thefatty phase and the emulsifier into a reaction vessel. The vessel isheated at a temperature of approximately 50 to 75° C., then the activeingredients and/or auxiliaries which are soluble in oil are added, andwater which has been heated beforehand to approximately the sametemperature and into which the water-soluble ingredients have optionallybeen dissolved beforehand is added with stirring. The mixture is stirreduntil an emulsion of the desired fineness is obtained, which is thenleft to cool to room temperature, if necessary with a lesser amount ofstirring.

According to a further preferred embodiment, the compositions accordingto the invention are a shower gel, a shampoo formulation or a bathpreparation.

Such formulations comprise at least one ampholytic copolymer or onepolyelectrolyte complex A) and customary anionic surfactants as basesurfactants and amphoteric and/or nonionic surfactants as cosurfactants.Further suitable active ingredients and/or auxiliaries are generallychosen from lipids, perfume oils, dyes, organic acids, preservatives andantioxidants, and thickeners/gel formers, skin conditioning agents andmoisturizers.

These formulations preferably comprise 2 to 50% by weight, preferably 5to 40% by weight, particularly preferably 8 to 30% by weight, ofsurfactants, based on the total weight of the formulation.

All anionic, neutral, amphoteric or cationic surfactants customarilyused in body-cleansing compositions can be used in the washing, showerand bath preparations.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefinsulfonates, in particular the alkali metal andalkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium,and ammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have between 1 and 10ethylene oxide or propylene oxide units, preferably 1 to 3 ethyleneoxide units, in the molecule.

These include, for example, sodium lauryl sulfate, ammonium laurylsulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate,sodium lauryl sarcosinate, sodium oleyl succinate, ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates, alkylamphodiacetates or amphodipropionates.

For example, cocodimethylsulfopropylbetaine, laurylbetaine,cocamidopropylbetaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mol permole of alcohol. Also suitable are alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols,ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan etheresters.

The washing, shower and bath preparations can also comprise customarycationic surfactants such as, for example, quaternary ammoniumcompounds, for example cetyltrimethylammonium chloride.

In addition, it is also possible to use other customary cationicpolymers, such as, for example, copolymers of acrylamide anddimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulosederivatives (Polyquaternium-4, -10), guar hydroxypropyltrimethylammoniumchloride (INCI: Hydroxylpropyl Guar Hydroxypropyltrimonium Chloride),copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole(Polyquaternium-16, -44, -46), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quarternized withdiethyl sulfate (Polyquaternium-11) and others.

The shower gel/shampoo formulations can further comprise thickeners,such as, for example, sodium chloride, PEG-55, propylene glycol oleate,PEG-120 methyl glucose dioleate and others, and also preservatives,further active ingredients and auxiliaries and water.

In a further preferred embodiment, the compositions according to theinvention are hair-treatment compositions.

Hair-treatment compositions according to the invention preferablycomprise at least one ampholytic copolymer or a polyelectrolyte complexA) in an amount in the range from about 0.1 to 30% by weight, preferably0.5 to 20% by weight, based on the total weight of the composition.

The hair-treatment compositions according to the invention arepreferably in the form of a setting foam, hair mousse, hair gel,shampoo, hairspray or hair foam.

Hairsprays include both aerosol sprays and also pump sprays withoutpropellant gas. Hair foams include both aerosol foams and also pumpfoams without propellant gas.

Preferred hair-treatment compositions are in the form of a gel or afoam. Such a hair-treatment composition comprises, for example:

-   a) 0.1 to 20% by weight, preferably 1 to 10% by weight, of at least    one ampholytic copolymer or polyelectrolyte complex A), as defined    above,-   b) 0.1 to 20% by weight, preferably 1 to 10% by weight, of at least    one water-soluble, for example neutral, polymer different from    component A)-   c) 0 to 40% by weight of at least one carrier (solvent) which is    chosen from C₂-C₅-alcohols, in particular ethanol,-   d) 0 to 5% by weight, preferably 0.01 to 5% by weight, particularly    preferably 0.2 to 3% by weight, of at least one thickener,-   e) 0 to 50% by weight of a propellant,-   f) 0 to 10% by weight, preferably 0.1 to 3% by weight, of at least    one setting polymer different from a), preferably a water-soluble    nonionic polymer,-   g) 0 to 1% by weight of at least one refatting agent, preferably    chosen from glycerol and glycerol derivatives,-   h) 0 to 30% by weight of further active ingredients and/or    auxiliaries, e.g. at least one silicone compound,-   i) water ad 100% by weight.

The hair-treatment compositions can also be in the form of hairsprays orhair foams. Hairsprays and hair foams preferably comprise predominantlyor exclusively water-soluble or water-dispersible components. If thecompounds used in the hairsprays and hair foams according to theinvention are water-dispersible, they can be used in the form of aqueousmicrodispersions with particle diameters of, usually, 1 to 350 nm,preferably 1 to 250 nm. The solids contents of these preparations arecustomarily in a range from about 0.5 to 20% by weight. Thesemicrodispersions generally do not require emulsifiers or surfactants fortheir stabilization.

Preferred hair-treatment compositions are in the form of an aqueousdispersion or in the form of an alcoholic or aqueous-alcoholic solution.Examples of suitable alcohols are ethanol, propanol, isopropanol andmixtures thereof.

Furthermore, the hair-treatment compositions according to the inventioncan generally comprise customary cosmetic auxiliaries, for examplesofteners, such as glycerol and glycol; emollients; perfumes;surfactants; UV absorbers; dyes; antistatic agents; agents for improvingcompatibility; preservatives; and antifoams.

If the compositions according to the invention are formulated ashairspray, they comprise a sufficient amount of a propellant, forexample a low-boiling hydrocarbon or ether, such as propane, butane,isobutane or dimethyl ether. Propellants which can be used are alsocompressed gases, such as nitrogen, air or carbon dioxide. The amount ofpropellant here can be kept low in order not to increase the VOC contentunnecessarily. This is then generally not more than 55% by weight, basedon the total weight of the composition. If desired, however, higher VOCcontents of 85% by weight and above are also possible.

The ampholytic copolymers according to the invention can also be used incombination with polyelectrolyte complexes according to the invention orin combination with other nonionic hair polymers in the compositions.Suitable polymers are those described above.

The other hair polymers are preferably present in amounts up to 10% byweight, based on the total weight of the composition.

A preferred hair-treatment composition in the form of a hairspraycomprises:

-   a) 0.3 to 20% by weight, preferably 0.5 to 10% by weight, in    particular 1 to 5% by weight, of at least one polymer A), as defined    above,-   b) 50 to 99.5% by weight, preferably 55 to 99% by weight, of a    carrier (solvent), chosen from water and water-miscible solvents,    preferably C₂-C₅-alcohols, in particular ethanol, and mixtures    thereof,-   c) 0 to 50% by weight, preferably 0.1 to 40% by weight, of a    propellant, preferably chosen from dimethyl ether and alkanes, such    as, for example, propane/butane mixtures,-   d) 0 to 10% by weight, preferably 0.1 to 10% by weight, in    particular 0.2 to 7% by weight, of at least one hair polymer    different from a), preferably a water-soluble or dispersible    polymer,-   e) 0 to 0.5% by weight, preferably 0.001 to 2% by weight, of at    least one water-soluble or water-dispersible silicone compound,    and optionally further active ingredients and/or auxiliaries, as    defined above.

The composition according to the invention can comprise, as componente), at least one nonionic, siloxane-containing, water-soluble or-dispersible polymer, in particular chosen from the polyethersiloxanesdescribed above. The proportion of this component is then generallyabout 0.001 to 2% by weight, based on the total weight of thecomposition.

The ampholytic copolymers or polyelectrolyte complexes A) are suitablein an advantageous manner as auxiliaries in pharmacy, for themodification of rheological properties (as thickener), as surface-activesubstance (polymeric emulsifier), preferably as or in (a) coating(s) forthe textile, paper, printing and leather industry.

The invention is described in more detail by reference to thenonlimiting examples below.

EXAMPLES

1. Preparation of Copolymers (Solution Polymerization)

Example 14 Copolymer of VP/MAM/DADMAC/DMAPMAM/MAA

Feed 1: Monomer mixture of: 300 g of vinylpyrrolidone 1200 g of a 15%strength aqueous solution of methacrylamide (=180 g of methacrylamideand 1020 g of water) 95 g of diallyldimethylammonium chloride 42 g ofdimethylaminopropylmethacrylamide 21 g of methacrylic acid Feed 2:Initiator solution of: 6 g of Wako V 50 [2,2′-azobis(2- amidinopropane)dihydrochloride] and 123 g of water Feed 3: Initiator solution of: 4 gof Wako V 50 [2,2′-azobis(2- amidinopropane) dihydrochloride] and 82 gof water

166 g of feed 1, 12.9 g of feed 2 and 137 g of water were initiallyintroduced into a stirred apparatus fitted with reflux condenser,internal thermometer and three separate feed devices, and the mixturewas heated to about 65° C. with stirring. Following the start ofpolymerization, recognizable when the viscosity starts to increase, at65° C., the remainder of feed 1 was added over the course of 3 h and theremainder of feed 2 over the course of 4 h, during which the internaltemperature was increased to about 68° C. When the addition wascomplete, the reaction mixture was stirred at 70° C. for about a further2 h. Feed 3 was then added at a temperature of 70° C. over the course of30 minutes and the polymer solution was then after-polymerized for abouta further 2 h at a temperature of about 80° C. The polymer solution wastreated with steam for 2 h. This gave an approximately 30% strengthpolymer solution.

For stabilization, the solution was treated with 100 ppm of Euxyl K100from Schülke and Mayr(5-chloro-2-methyl-3-(2)-isothiazolone/2-methyl-3-(2H)-isothiazolone/benzylalcohol).

Pulverulent products were obtained by spray-drying or freeze-drying.

The polymers 1 to 13 were prepared analogously.

2. Preparation of Copolymers (Precipitation Polymerization)

Example 15 Copolymer of VP/VFA/DADMAC/DMAPMAM/MAA/DATDA

Feed 1: Monomer mixture of: 240 g of vinylpyrrolidone 240 g ofvinylformamide 105 g of 60% strength diallyldimethylammonium chloride(63 g and 42 g of water) 36 g of dimethylaminopropylmethacrylamide 18 gof methacrylic acid 6 g of 50% strength diallyltartardiamide (3 g and 3g of water)

Feed 2: Initiator solution of: 1.8 g of Wako V 50 [2,2′-azobis(2-amidinopropane) dihydrochloride] and 25 g of ethyl acetate

65 g of feed 1 and 2.7 g of feed 2 in 1370 g of ethyl acetate wereinitially introduced into a stirred apparatus fitted with refluxcondenser, internal thermometer and two separate feed devices and themixture was heated to about 75° C. with stirring. After the start ofpolymerization, recognizable from slight clouding, the remainder of feed1 was added over the course of 3 hours and the remainder of feed 2 overthe course of 4 hours, during which the internal temperature wasincreased to about 78° C. The reaction solution was stirred furtherunder reflux for two hours. The product precipitated out in the form ofa fine powder. After cooling, the polymer was filtered off with suction,washed three times with acetone and dried overnight in a drying cabinetat 40° C. under reduced pressure.

The polymers No. 16-30 were prepared analogously.

TABLE 1 DADMA DMAP- DATD VP Vcap MAM VFA C MAM:MAA VI:AA A MBAA [% by [%by [% by [% by [% by [% by [% by [% by [% by wt.] wt.] wt.] wt.] wt.]wt.] wt.] wt.] wt.] 1 70 27 — — — — 2.5:0.5 — — 2 70 — 26 — — — 3:1 — —3 70 — 26 — — 3:1 — — 4 60 37 — — — — 2.5:0.5 — — 5 60 — 37 — — —2.5:0.5 — — 6 60 — 37 — — 2.5:0.5 — — 7 60 — 35.5 — — 3:1.5 — — — 8 60 —35.5 — 3:1.5 — — — 9 60 29.5 — — — 7:3.5 — — — 10 60 — 29.5 — — 7:3.5 —— — 11 80 — — — 9.5 7:3.5 — — — 12 60 — 20 — 9.5 —   8:2.5 — — 13 50 —30 — 9.5 7:3.5 — — — 14 40 — — 40 9.5 —   8:2.5 — — 15 40 — — 40 10.56:3   — 0.5 — 16 30 — — 30 19.5 13:7   — 0.5 — 17 30 — — 30 9.5 20:10  — 0.5 — 18 26 — — 40 9.5 — 18:6  — 0.5 19 — — — 64.5 5 — 23:7  — 0.5 20— — — 64.5 5 20:10   — — 0.5

TABLE 2 SMA DMAP- MBAA VP Vcap [% by VFA MAM:MAA [% by [% by wt.] [% bywt.] wt.] [% by wt.] [% by wt.] wt.] 21 63.8 — — — 24:12 0.2 22 40 23.8— — 24:12 0.2 23 40 — — 23.8 24.12 0.2 24 — 23.8 — 40 24:12 0.2 25 — — —63.8 24:12 0.2 26 52 — 2.8 — 30:15 0.2 27 30 22 2.8 — 30:15 0.2 28 30 —2.8 22 30:15 0.2 29 — 30 2.8 22 30:15 0.2 30 — — 2.8 52 30:15 0.2 VP =vinylpyrrolidone Vcap = vinylcaprolactam MAM = methacrylamide VFA =vinylformamide DADMAC = diallyldimethylammonium chloride DMAPMAM =dimethylaminopropylmethacrylamide MAA = methacrylic acid VI =vinylimidazole AA = acrylic acid DATDA = N,N′-diallyltartardiamide MBAA= methylbisacrylamide SMA = stearyl methacrylate3. Application Examples

Use in HAIR Cosmetics:

1) Hair gels containing an anionic thickener: example Nos 21-28

[%] CTFA Phase 1: Polymer 1-8 (30% strength aqueous 10.0 solution)Glycerol 0.3 Water dist. 39.2 Further additives: preservatives, solubleethoxylated silicone, perfume q.s. Phase 2: Carbopol 940 (1% strengthaqueous 30.0 Carbomer suspension) Triethanolamine 0.5 Water dist. 20.0

To prepare hair gels, the components are weighed in and homogenized.Phase 2 forms a clear, solid gel into which phase 1 is slowly stirred.

2) Hair gels containing a further setting polymer and anionic thickener:example Nos 29-36

[%] CTFA Phase 1: Polymer 1-8 (30% 7.0 strength aqueous solution)Luviskol VA 64 1.0 Vinylpyrrolidonevinyl acetate copolymer Belsil DMC 6031 0.1 ethoxylated polydimethylsiloxane Uvinul MS 40 0.2 Benzophenone-4Glycerol 0.1 D-Panthenol USP 0.1 Panthenol Ethanol 20.0 Water dist. 21.0Further additives: q.s. preservatives, soluble ethoxylated silicone,perfume Phase 2: Carbopol 940 (1% 30.0 Carbomer strength aqueoussuspension) Triethanolamine 0.5 Water dist. 20.0

Preparation: The components of the two phases are homogenized afterbeing weighed in. Phase 2 forms a clear, solid gel. Phase 1 is slowlystirred into phase 2.

3) Liquid Hair Gels: Example Nos 37-50

[%] CTFA Polymer 1-14 (30% strength 5.3 aqueous solution) Natrosol 250 L(2% strength 25.0 Hydroxyethyl cellulose aqueous solution) (Hercules)C-Dry MD 1915 (10% strength 25.0 Degraded starch aqueous solution)(Cerestar) Water dist. 44.7 Further additives: preservatives, q.s.soluble ethoxylated silicone, perfume

Preparation: Weigh in and slowly homogenize at room temperature.

4) Cationic Self-Thickening Hair Gels (Without Additional Thickener):Example Nos. 51-56

[%] CTFA Phase 1: Polymer 15-20 3.0 (in powder form) Glycerol 0.1 Waterdist. 96.6 Further additives: q.s. preservatives, soluble ethoxylatedsilicone, perfume Phase 2: 45% strength phosphoric acid

Preparation: The components of phase 1 are weighed in, homogenized at40° C. and then phase 2 is added with stirring until a pH of 5.5 to 6was reached.

5) Anionic self-thickening hair gels (without additional thickener):example Nos. 57-60

[%] CTFA Phase 1: Polymer 17-20 3.0 (in powder form) Glycerol 0.1 Waterdist. 96.9 Further additives: q.s. preservatives, soluble ethoxylatedsilicone, perfume Phase 2: Aminomethylpropanol (45% strength aqueoussolution)

Preparation: The components of phase 1 were weighed, homogenized at 40°C. and then phase 2 was added with stirring until a pH of 8.5 wasreached.

4. Preparation of Copolymers Based on2-acrylamido-2-methylpropanesulfonic Acid

General preparation procedure: Solution polymerization in ethanol/water(1:1)

Example 60

500 g of a 30% strength polymer solution (AMPS/Na AMPS/DMAPMAM/VP/fattyalcohol ethoxylate MA)

Feed 1: Monomer mixture of: 120 g of vinylpyrrolidone 7.5 g ofC₁₆/C₁₈-fatty alcohol ethoxylate methacrylate (25 EO) 7.5 g of2-acrylamido-2- methylpropanesulfonic acid (AMPS) 7.5 g of AMPS sodiumsalt 7.5 g of dimethylaminopropylmethacrylamide Feed 2: Initiatorsolution of: 0.3 g of Wako ® 50 [2,2′-azobis(2- amidinopropane)dihydrochloride] 105 g of water Feed 3: Initiator solution of: 0.75 g oftert-butyl perpivalate, 75% strength 61.5 g of ethanol Feed 4: 1 g ofNaOH 28 g of water

11 g of feed 1, 5 g of feed 2, 70 g of water and 44 g of ethanol wereinitially introduced into a stirred apparatus fitted with refluxcondenser, internal thermometer and four separate feed devices, and themixture was heated to about 70° C. with stirring. Following the start ofpolymerization, recognizable from a slight increase in the viscosity, at70° C., the remainder of feed 1 was added over the course of three hoursand the remainder of feed 2 over the course of four hours, during whichthe internal temperature was increased to about 73° C. The reactionsolution was then further stirred for about two hours at 70° C. and thenfeed 3 was metered in over the course of 30 minutes at 70° C. Followingthe addition, the mixture was after-polymerized for about a further twohours at a temperature of 80° C. The polymer solution was adjusted to pH8 with NaOH solution (feed 4, addition time 10 minutes). This gave anapproximately 30% strength aqueous/ethanolic solution.

The polymers Nos. 31-59 and 61-80 were prepared analogously.

TABLE 3 Plex Neutralized VP MAM AMPS DMAPMAM VI NtBAEMA FAEMA 6877-0 topH Ex. No. [% by wt.] [% by wt.] [% by wt.] [% by wt.] [% by wt.] [% bywt.] [% by wt.] [% by wt.] MBAA 6-8 with 31 98 — 0.55 0.45 — — 1.0 — —AMP 32 97 — 0.65 — 0.35 — 2.0 — — AMP 33 97 — 0.55 0.45 — — 2.0 — — AMP34 96.5 — 0.55 — — 0.45 2.5 — — AMP 35 95 — 1.1 0.9 — — 3.0 — — AMP 3694 — 0.55 0.45 — — 5.0 — — AMP 37 90 — 3.4 — 1.6 — 5.0 — — AMP 38 90 —2.7 2.3 — — 5.0 — — AMP 39 90 — 2.7 — — 2.3 5.0 — — AMP 40 87 — 3.4 —1.6 — 8.0 — — AMP 41 87 — 2.7 2.3 — — 8.0 — — AMP 42 85 — 5.4 4.6 — —5.0 — — NaOH***) 43 75 — 11 9 — — 5.0 — — NaOH***) 44 70 — 11 9 — — 10.0— — NaOH***) 45 55 — 22 18 — — 5.0 — — NaOH***) 46 77 20 0.55 0.45 — —2.0 — — AMP 47 65 30 1.1 0.9 — — 3.0 — — AMP 48 60 30 3.4 — 1.6 — 5.0 —— AMP 49 55 30 5.4 4.6 — — 5.0 — — AMP 50 94 — 0.55 0.45 — — — 5.0 — AMP51 91 — 0.55 0.45 — — — 8.0 — AMP 52 79 — 0.55 0.45 — — — 20 — AMP 53 75— 3.4 — 1.6 — — 20 — AMP 54 70 — 5.4 4.6 — — — 20 — AMP 55 55 36 0.550.45 — — — 8.0 — AMP 56 50 25 3.4 1.6 — — — 20 — AMP 57 96 — 0.3/0.9*)0.3 — — 2.5 — — NaOH 58 93.5 — 0.3/0.9*) 0.3 — — 5.0 — — NaOH 59 85 —2.5/5.0*) 2.5 — — 5.0 — — NaOH 60 80 — 5.0/5.0*) 5.0 — — 5.0 — — NaOH 6180 — 6.5/5.0*) — 3.5 — 5.0 — — NaOH 62 70 —  6.5/15.0*) — 3.5 — 5.0 — —NaOH 63 88.5 — 0.3/0.9*) 0.3 — — — 10 — NaOH 64 78.5 — 0.3/0.9*) 0.3 — —— 20 — NaOH 65 70 — 2.5/5.0*) 2.5 — — — 20 — NaOH 66 65 — 5.0/5.0*) 5.0— — — 20 — NaOH 67 95 — 0.4 — 0.3/3.3**) — 1.0 — — AMP 68 97.5 — 3.0 —2.0/5.0**) — 2.5 — — AMP 69 70 — 6.5 — 3.5/15**)  — 5.0 — — AMP 70 81 —0.4 — 0.3/8.3**) — — 10 — AMP 71 60 — 1.0 —  0.6/18.4**) — — 20 — AMP 7296.5 — 0.5 0.4 0.4 — 2.5 — 0.1 AMP 73 90 — 2.65 2.3 2.3 — 5.0 — 0.05 AMP74 85 — 6.5 — — — 5.0 — 0.07 AMP 75 85 — 3.5/4.0*) — — — 5.0 — 0.07 AMP76 89 — 0.5 0.4 0.4 — — 10 0.1 AMP 77 75 — 2.65 2.3 2.3 — — 20 0.05 AMP78 70 —  3.0/3.93*) 3.0 3.0 — — 20 0.07 AMP 79 55 34 0.5 0.4 0.4 — — 100.1 AMP 80 50 25 2.65 2.3 2.3 — — 20 0.05 AMP VP = vinylpyrrolidone MAM= methylacrylamide AMPS = 2-acrylamido-2-methylpropanesulfonic acid *)=AMPS sodium salt DMAPMAM = dimethylaminopropylmethacrylamide VI =vinylimidazole **)= VI quaternized with dimethyl sulfate NtBAEMA =tert-Butylaminoethyl methacrylate FAEMA = C₁₆/C₁₈-fatty alcoholethoxylate methacrylate (25 EO) Plex 6877-0 = Mixture of 25% by weightof C₁₆/C₁₈-fatty alcohol ethoxylate methacrylate (25 EO) and 75% byweight of methyl methacrylate (Rohm) MBAA = Methylenebisacrylamide AMP =2-Amino-3-methylpropanol ***)firstly adjusted to a pH of >8 with NaOH,then adjusted to pH 6-8 by adding lactic acidApplication Examples:

Use in Hair Cosmetics:

1. Conditioner shampoo (example Nos. 81-130)

[%] A) Texapon NSO 28% strength 50.0 (Sodium laureth sulphate/Henkel)Comperlan KD (coamide DEA/Henkel) 1.0 Polymer 31-80 3.0 (20% aqueoussolution) Water 17.0 q.s. perfume oil 27.5 B) Water 27.5 Sodium chloride1.5 q.s. preservative . . .

-   -   Preparation: weigh in and dissolve and mix phases A and B        separately with stirring, slowly stir phase B into phase A.        2. Setting foam: (examples 131-180)

[%] Polymer 31-80 5.0 (20% strength aqueous solution) Cremophor A 25(Ceteareth 25/BASF) 0.2 Comperlan KD (coamide DEA/Henkel) 0.1 Water 84.7Dimethyl ether 3.5 bar (20° C.) 10.0 Further additive: perfume,preservative . . .

-   -   Preparation: weigh in and dissolve with stirring, bottle and add        propellant gas.        3. Hair Gels with an Anionic Thickener: (Examples Nos. 181-230)

[%] CTFA Phase 1: Polymer 31-80 15.0 (20% strength solution) Glycerol0.3 Water, dist. 34.2 2-Amino-2-methylpropanol to pH 8 Further additive:preservative, soluble ethoxylated silicone, perfume . . . Phase 2:Aculyn 28 (1% strength 50.0 aqueous suspension) 2-Amino-2-methylpropanol0.5

-   -   Preparation: weigh in and homogenize. A clear solid gel forms in        phase 2. Slowly stir phase 1 into phase 2.        4. Hair gels with a further setting polymer and thickener:        (examples Nos. 231-280)

[%] CTFA Phase 1: Polymer 31-80 (20% strength 7.0 aqueous solution)Luviset Clear ® 1.0 VP/Methacry- lamide/Vinyl- imidazole copolymerBelsil DMC 6031 0.1 ethoxylated polysiloxane (Goldschmidt) Uvinul MS 400.2 Benzophenone-4 Glycerol 0.1 D-Panthenol USP 0.3 Panthenol Ethanol10.0 Water, dist. 31.0 Further additive: preservative, solubleethoxylated silicone, perfume . . . Phase 2: Acuyln 28 (1% strengthaqueous 30.0 suspension) 2-Amino-2-methylpropanol 0.3 Water, dist. 20.0

Preparation: weigh in and homogenize. Slowly stir phase 1 into phase 2.A clear solid gel forms in phase 2.

5. Anionic Self-Thickening Hair Gels

(Example Nos. 281-330) (Without Additional Thickener):

[%] CTFA Polymer 31-80 (20% strength 10.0 aqueous solution) LuvisetClear ® 2.0 VP/Methacry- lamide/Vinyl- imidazole copolymer Uvinul MS 400.2 Benzophenone-4 D-Panthenol USP 0.3 Panthenol Water, dist. 57.5Further additive: preservative, soluble ethoxylated silicone, perfume .. .

-   -   Preparation: weigh in and homogenize. The polymer solution is        then adjusted to pH 7.5 with 2-amino-2-methylpropanol (25%        strength). A viscous clear gel is formed.        Use in Skin Cosmetics:        6. Standard O/W Cream: (Examples Nos. 331-380)

% CTFA name Oil phase Cremophor A6 3.0 Ceteareth-6- (and) Stearylalcohol Ceteareth-25 Cremophor A25 3.0 Glyceryl Stearate Glycerolmonostearate s.e. 2.5 Paraffin oil Paraffin oil Cetyl alcohol 7.5 Cetylalcohol Luvitol EHO 3.5 Cetearyl octanoate Vitamin E acetate 3.2Tocopherol acetate Nip-Nip 1.0 Methyl and propyl-4-hydroxy- 0.1 benzide(7:3) Water phase: Polymer 31-80 3.0 (20% strength aqueous solution)Water 74.6 Water 1,2-Propylene glycol 1.5 Propylene Glycol Germall II0.1 Imidazolidinylurea

Preparation: Weigh in and homogenize the oil phase and water phaseseparately with stirring at a temperature of about 80° C. Slowly stirthe water phase into the oil phase. Slowly cool to room temperature withstirring.

We claim:
 1. An ampholytic copolymer obtained by free-radicalcopolymerization of a) at least one compound with a free-radicallypolymerizable, α,β-ethylenically unsaturated double bond and at leastone anionogenic and/or anionic group per molecule selected from thegroup consisting of acrylic acid, methacrylic acid and2-acrylamido-2-methylpropanesulfonic acid, b) at least one compound witha free-radically polymerizable, α,β-ethylenically unsaturated doublebond and at least one cationogenic and/or cationic group per moleculeselected from the group consisting of vinylimidazole,tert.-butylaminoethyl methacrylate and mixtures thereof, and, c) atleast one α,β-ethylenically unsaturated amide-group-containing compoundselected from the group consisting of acrylamide, methacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamideand mixtures thereof, where the quantitative molar ratio of compounds a)to compounds b) is from 0.5:1 to less than 2:1.
 2. A polyelectrolytecomplex comprising at least one ampholytic copolymer, as defined inclaim 1, and at least one further polyelectrolyte different therefrom.3. The ampholytic copolymer as claimed in claim 1, where thequantitative molar ratio of compounds a) to compounds b) is in a rangefrom 0.7:1 to 1.8:1.
 4. The composition as claimed in claim 1, where atleast some of the compounds a) and b) are used in the form of a monomercomposition, where the molar ratio of anionogenic groups of component a)to cationogenic groups of component b) is about 1:1.
 5. The compositionas claimed in claim 1, which additionally comprises, in copolymerizedform, at least one further monomer d) selected from the group consistingof esters of α,β-ethylenically unsaturated mono- and dicarboxylic acidswith C₁-C₃₀-alkanols and C₁-C₃₀-alkanediols, amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids withC₂-C₃₀-aminoalcohols which have a primary or secondary amino group,N-alkyl- and N,N-dialkylamides of α,β-ethylenically unsaturatedmonocarboxylic acids which, in addition to the carbonyl carbon atom ofthe amide group, have more than 8 further carbon atoms, esters of vinylalcohol and allyl alcohol with C₁-C₃₀-monocarboxylic acids, vinylethers, vinylaromatics, vinyl halides, vinylidene halides,C₁-C₈-monoolefins, nonaromatic hydrocarbons with at least two conjugateddouble bonds, siloxane macromers and mixtures thereof.
 6. Thecomposition as claimed in claim 1, which additionally comprises, ascomponent e), at least one polyether acrylate in copolymerized form. 7.The composition as claimed in claim 1, which is obtainable byfree-radical copolymerization in the presence of a component g) which isselected from the group consisting of g1) polyether-containingcompounds, g2) polymers which have at least 50% by weight of repeatunits which are derived from vinyl alcohol, g3) cellulose, starch andderivatives thereof, and mixtures thereof.
 8. The composition as claimedin claim 1, which additionally comprises, in copolymerized form, atleast one free-radically polymerizable crosslinking compound f) with atleast two α,β-ethylenically unsaturated double bonds per molecule.